Cleaning product which uses sonic or ultrasonic waves

ABSTRACT

The present invention relates to compositions, product kits, devices and processes for removing using sonic or ultrasonic waves with ultrasonically enhanced cleaning agents.

This application claims the benefit of No. 60/108,547 filed Nov. 16,1998.

FIELD OF THE INVENTION

The present invention generally relates to compositions, product kits,devices and processes for removing using sonic or ultrasonic waves.

BACKGROUND OF THE INVENTION

Ultrasonic cleaning is a well known cleaning process in industry. Forexample, it is used to clean electronic components after or duringimmersion in cleaning solution such as azeotropic mixtures offlurohydrocarbons. It is also used domestically to a small extent inoral hygiene, as in ultrasonic tooth brushes. However, ultrasoniccleaning has not found much acceptance domestically beyond this limitedapplication.

While ultrasonics do give good cleaning in these limited applicationsthere has been no truly breakthrough cleaning performance from thecombination of ultrasonic or sonic energy with conventional cleaningadditives. Many and varied combinations have been tried resulting ineither insignificant cleaning benefits or additional problems which makeany benefits impracticable.

Accordingly there remains in the art the search for a cleaningingredient or ingredients which will provide surprisingly and unexpectedsuperior cleaning when used in conjunction with ultrasonic or sonicenergy.

BACKGROUND ART

U.S. Pat. Nos. 5,464,477, 5,529,788, 4,308,229, 4,448,750; WO 94/07989,WO 97/16263, WO 94/23852, WO 93/06947; GB 2,204,321; EP 258,819; DE4,100,682; JP 10036892, JP 08157888.

SUMMARY OF THE INVENTION

It has now been surprisingly found that certain specific ingredient oringredients which will provide surprisingly and unexpected superiorcleaning when used in conjunction with ultrasonic or sonic energy. Thesecleaning ingredients are called ultrasonically enhanced cleaning agentsand are selected from bleach catalysts, amylase enzymes and mixturesthereof.

The present invention also includes ultrasonic cleaning products whichcomprise:

(a) a cleaning composition comprising an ultrasonically enhancedcleaning agent selected from the group consisting of amylase enzyme,bleach catalyst and mixtures thereof; and

(b) a sonic or ultrasonic wave generating source for imparting sonic orultrasonic waves.

The present invention also comprises a process for removing tough foodfrom a hard surface comprising the steps of:

(i) applying an effective amount of a cleaning composition to said toughfood on said hard surface, said cleaning composition comprises anultrasonically enhanced cleaning agent selected from the groupconsisting of amylase enzyme, bleach catalyst and mixtures thereof; and

(ii) imparting sonic or ultrasonic waves to said tough food so as toremove said tough food from said hard surface.

As used herein, the phrase “ultrasonic waves” means mechanical pressureor stress waves which can propagate through any material media, whereinthe frequency spectra of these waves can vary from a few cycles/second(Hz) to a few billion Hz.

All percentages, ratios and proportions herein are by weight, unlessotherwise specified. All documents cited are, in relevant part,incorporated herein by reference.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a perspective view of a hand-held, ultrasonic device, with acleaning solution storage means which is adapted to be removably mountedin the device. Also shown are a removably mountable cleaning head and anadditional cleaning solution storage means.

FIG. 2 is a perspective view of two different hand-held, pen-shapedultrasonic devices, which are used in the invention to impart ultrasonicwaves onto a stain or soil.

FIG. 3 is a perspective view of a hand-held, pen-shaped ultrasonicdevice, which is shown imparting ultrasonic waves onto a soil.

FIG. 4 is a perspective an ultrasonic device, which are used in theinvention to impart ultrasonic waves onto a stain or soil. Theultrasonic generator and the power source are in a second housing whichis associated with the cleaning head which is in a first housing.

DETAILED DESCRIPTION OF THE INVENTION

As it was stated previously, the present invention also includesultrasonic cleaning products which comprise:

(a) a cleaning composition, preferably a liquid or gel, comprising anultrasonically enhanced cleaning agent selected from the groupconsisting of amylase enzyme, bleach catalyst and mixtures thereof, and

(b) a sonic or ultrasonic wave generating source for imparting sonic orultrasonic waves.

Preferably the ultrasonically enhanced cleaning agents is present in thecleaning composition in an effective amount, more preferably from about0.0001% to about 40%, even more preferably from about 0.001% to about20%, even more preferably still from about 0.005% to about 10%, evenmore preferably still from about 0.01% to about 5% by weight. It hasbeen surprisingly found that these ultrasonically enhanced cleaningagents deliver increased cleaning performance when they are used incleaning in conjunction with ultrasonic or sonic energy. These cleaningcompositions can comprise additional cleaning additives and these areexemplified in greater detail hereafter.

In another aspect the cleaning composition can be a hand dishwashingcomposition (a so called LDL), a hard surface cleaner, an automaticdishwashing composition. Alternatively the cleaning composition could bea composition specifically formulated for use in ultrasonic cleaning, socalled UCC or ultrasonic cleaning compositions. Furthermore, thecleaning composition could be just an ultrasonically enhanced cleaningagent alone or with one or more conventional cleaning agents which donot resemble any of these conventional cleaning compositions mentionedpreviously.

The cleaning composition in the ultrasonic cleaning products can be, forexample, in a storage means in the ultrasonic device, in anothercontainer in the same product and designed to be added to the storagemeans in the ultrasonic device before use, in another container in thesame product and directly added to the surface to be cleaned, in anothercontainer in the same product and made into an aqueous solution in whichthe surface is immersed, in another container in the same product andapplied to by the user from another container to the cleaning surface ofthe ultrasonic device either neat or as an aqueous solution, or inanother container in the same product as an aqueous solution. These aremerely some possible examples and not intended to be limiting.

In one aspect the ultrasonically enhanced cleaning agent is a bleachcatalyst and is preferably selected from the group consisting ofmanganese bleach catalysts, cobalt bleach catalysts, iron bleachcatalysts and mixtures thereof.

It is believed that, while not wanting to be limited by theory, that theultrasonic energy improves the rehydration of the soil and hence makesit easier to clean. It is believed to do this by increasing the surfacearea of the emulsion by either forming cracks or increasing the size ofcracks already present, in the soil. This gives the cleaning solution agreater surface area to rehydrate the soil.

By using this composition with a source of ultrasonic energy, stains ortough soils can be removed without the use of excessive force, rubbing,pressure or other manipulation which causes wear and tear on the stainedmaterial or surface. In doing so, the user does not need to impart suchmanual energy to remove the stain, thereby adding to the convenience ofthe user. The invention also encompasses processes by which such stainsor soils are removed, either from localized regions or from the entirearticle to be cleaned.

The present application also includes methods of washing tableware andhard surfaces by either applying a neat or aqueous solution to the soilor stain, to be removed form the surface and the imparting ultrasonic orsonic waves to the soil or stain. Furthermore, the present applicationalso includes methods of washing tableware by contacting the tablewarewith an aqueous solution, such as by immersion in an aqueous solution,then imparting sonic or ultrasonic waves to said soiled tableware. It ispreferred that the surface be a hard surface. A “hard surface” is anysurface which is traditionally regarded as hard, that is tableware, suchas plates, glasses, cutlery, pots and pans, and also includes othersurfaces such as kitchen counter tops, sinks, glass, windows, enamelsurfaces, metal surfaces, tiles, bathtubs, floors etc. More preferably,the hard surface is tableware.

It is preferred that these ultrasonic cleaning products further compriseinstructions for using the product. One preferred set of instructionscomprises the steps of

(i) applying an effective amount of said cleaning composition to saidsurface;

(ii) imparting sonic or ultrasonic waves to said surface using saiddevice; and

(iii) optionally, rinsing the surface with an aqueous solution.

Another, preferred set of instructions comprise the steps of:

(i) using said device to apply an effective amount of said cleaningcomposition to said surface concurrently and coterminous with saidcleaning head;

(ii) moving said cleaning head over and maintain contact thereto saidsurface and

(iii) optionally, rinsing the surface with an aqueous solution.

As it was stated previously, The present invention also comprises aprocess for removing tough food from a hard surface comprising the stepsof:

(i) applying an effective amount of a cleaning composition to said toughfood on said hard surface, said cleaning composition comprises anultrasonically enhanced cleaning agent selected from the groupconsisting of amylase enzyme, bleach catalyst and mixtures thereof; and

(ii) imparting sonic or ultrasonic waves to said tough food so as toremove said tough food from said hard surface; and

(iii) optionally, rinsing said hard surface with an aqueous solution.

In one aspect of this it is preferred that steps (i) and (ii) areconducted simultaneously using a device that permits controlleddispensing of said liquid cleaning composition to the stain whileconcurrently imparting sonic or ultrasonic waves thereto.

The source of ultrasonic or sonic energy or waves can be from anysuitable source. A variety of sonic or ultrasonic sources can be used inthe invention including, but not limited to, sonic cleaning bathstypically used to clean jewelry and sonic toothbrushes for cleaningteeth. This includes basins or sinks, such as the Branson UltrasonicBath, ultrasonic “balls”, which are dropped into a conventional sink orbasin, such as the Sonic Wash Ball by “D&P Wash Machine”, baskets orracks into which the item to be cleaned is placed ant this is thenplaced into a conventional sink or basin. Alternatively, the source ofultrasonic energy could be provided by a modified ultrasonic toothbrush, such as the Teldyne Water Pik model SR-400R. It is one preferredaspect that sonic or ultrasonic source is a, hand-held vibrationalultrasonic device with a cleaning head one distal end of said device. Itis another preferred aspect that in ultrasonic cleaning product thecleaning composition and the sonic or ultrasonic source contained intogether in a device that permits controlled dispensing of the cleaningcomposition to a hard surface in need of cleaning, while concurrentlyimparting sonic or ultrasonic waves thereto.

In one aspect of the present invention the acoustic system, whichgenerates the sonic or ultrasonic waves is made from a piezo ceramicelement or elements, typically called PZTs, along with an acousticamplifier, typically called an acoustic horn or acoustic transducer orsonotrode. The entire acoustic system is designed to operate at aspecific frequency and power and deliver a predetermined amplitude atthe end or tip of the sonotrode. The combination of the sonotrodedesign, amplitude, frequency and power dictates the cleaning efficacy.Further, not all of the parameters are independently choosen.

With regards to the design of the sonotrode, a variety of differentshapes provide improved cleaning benefits. One specific embodiment is a“chisel” design, where the sonotrode is tapered at the end which willcontact, or be proximate to, the stain/soil to be removed. Typically,the width of the sonotrode is much less than its length. For example thesonotrode may be 0.05 to 5 mm wide and the is 10 to 50 mm long. In oneembodiment, cleaning is improved when the sonotrode is designed todeliver equal amplitude across the sonotrode blade. However, there areother embodiments where having a higher localized amplitude is prefered.In one embodiment, it has surprisingly been found that a sonotrode bladein a “chisel” shape running at 50 kHz, 30 Watts and 40 microns providessignificant cleaning benefits.

In another embodiment, it has surprisingly been found that sonotrodesdesigned in a “disc” or round shape deliver significant cleaningbenefits. This sonotrode embodiment typically has a disc radius of from10 to about 100 mm. Further, the sonotrode may present a more threedimensional appearance to the stain/soil to be cleaned. The sonotrodemay be in the shape of a hemisphere or may be disc shaped withundulations or dimples on the surface. In another embodiment, thesonotrode can be rectangular, oval, triangular shaped. Because ofergonomic considerations, it is preferred that the sonotrode haverounded edges. Each of these different embodiments offers uniquecleaning opportunities. In addition, the mass of the sonotrode isimportant to achieve the desired cleaning benefit. It has surprisinglybeen found that the sonotrode must have a mass between 20 and 500 grams.

Further, the sonotrode material must be chosen to have the desiredacoustic properties and also be compatible with the chemistry being usedin the cleaning application. Suitable materials include titanium,aluminum and steel, preferably hardened steel. Less preferred, butacceptable for cleaners which are substantially free from bleaches andalkalinity is aluminum.

In another aspect of the present invention the acoustic system and inparticular the sonotrode may be encased, surrounded, or in closeproximity to adjunct materials to aid in the cleaning process. Theseinclude, but are not limited to, sponges, scouring pads, steel woolpads, high friction non-wovens, and absorbent natural and syntheticmaterials. These adjunct materials can help cleaning by removing thesoils and stains that are loosened by the ultrasonic plus chemistry,and/or they can act to absorb residual stains and/or hold the cleaningsolution in close contact with the stain or soil which is in contactwith the ultrasonic energy. Optionally, these adjunct pads can beremovable and/or disposable.

Another possible ultrasonic generation device is that of copendingapplication U.S. Ser. No. 60/180,629, filed on Nov. 16, 1998.

The transducer means oscillates at a frequency of from about 100 Hz toabout 20,000 kHz, more preferably from about 100 Hz to about 10,000 kHz,more preferably from about 150 Hz to about 2000 kHz, more preferablyfrom about 150 Hz to about 1,000 kHz, more preferably from about 150 Hzto about 100 kHz, more preferably from about 200 Hz to about 50 kHz. Itis preferred that the average frequency be from about 1000 Hz to about100 kHz, more preferably from about 10,000 Hz to about 70 kHz. It isalso preferred that the device provides a power output per unit ofsurface area of said cleaning head of at least about 0.02 watts/cm²,more preferably at least about 0.05 watts/cm², even more preferably atleast about 0.07 watts/cm², even more preferably still at least about0.08 watts/cm².

Typical treatment times range from about 1 second to about 5 minutes,more typically from about 20 seconds to about 2 minutes, and mosttypically from about 30 seconds to 1 minute, although treatment timeswill vary with the severity of the stain or toughness of the soil. Thesonic or ultrasonic source device can be a vibrational sonic orultrasonic generator, a torsional sonic or ultrasonic wave generator, oran axial sonic or ultrasonic generator in that it is the shock wavesgenerated by these sonic or ultrasonic sources that does the actualcleaning or loosening of the stain on the textile regardless of themechanism by which the sonic or ultrasonic shock waves are generated.The sonic or ultrasonic wave generating device can be battery operatedor a plug-in type.

Cleaning Compositions

The compositions herein include one or more ultrasonically enhancedcleaning agents. It is preferred that the compositions further containone or more conventional cleaning agents for assisting or enhancingcleaning performance, treatment of the substrate to be cleaned, or tomodify the aesthetics of the detergent composition (e.g., perfumes,colorants, dyes, etc.). The following are illustrative examples of suchadjunct materials.

Ultrasonically Enhanced Cleaning Agent—these are selected from amylaseenzymes, bleach catalysts and mixtures thereof. These ultrasonicallyenhanced cleaning agents may optionally be combined with one ore moreconventional cleaning additives.

Amylase—Amylases (α and/or β) can be included for removal ofcarbohydrate-based stains. Suitable amylases are Termamyl® (NovoNordisk), Fungamyl® and BAN® (Novo Nordisk). The enzymes may be of anysuitable origin, such as vegetable, animal, bacterial, fungal and yeastorigin. Amylase enzymes are normally incorporated in the detergentcomposition at levels from 0.0001% to 2%, preferably from about 0.0001%to about 0.5%, more preferably from about 0.0005% to about 0.1%, evenmore preferably from about 0.001% to about 0.05% of active enzyme byweight of the detergent composition.

Amylase enzymes also include those described in WO95/26397 and incopending application by Novo Nordisk PCT/DK96/00056. Other specificamylase enzymes for use in the detergent compositions of the presentinvention therefore include:

(a) α-amylases characterised by having a specific activity at least 25%higher than the specific activity of Termamyl® at a temperature range of25° C. to 55° C. and at a pH value in the range of 8 to 10, measured bythe Phadebas® α-amylase activity assay. Such Phadebas® α-amylaseactivity assay is described at pages 9-10, WO095/26397.

(b) α-amylases according (a) comprising the amino sequence shown in theSEQ ID listings in the above cited reference, or an α-amylase being atleast 80% homologous with the amino acid sequence shown in the SEQ IDlisting.

(c) α-amylases according (a) obtained from an alkalophilic Bacillusspecies, comprising the following amino sequence in the N-terminal:His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp.

A polypeptide is considered to be X% homologous to the parent amylase ifa comparison of the respective amino acid sequences, performed viaalgorithms, such as the one described by Lipman and Pearson in Science227, 1985, p. 1435, reveals an identity of X%.

(d) α-amylases according (a-c) wherein the α-amylase is obtainable froman alkalophilic Bacillus species; and in particular, from any of thestrains NCIB 12289, NCIB 12512, NCIB 12513 and DSM 935.

In the context of the present invention, the term “obtainable from” isintended not only to indicate an amylase produced by a Bacillus strainbut also an amylase encoded by a DNA sequence isolated from such aBacillus strain and produced in an host organism transformed with saidDNA sequence.

(e) α-amylase showing positive immunological cross-reactivity withantibodies raised against an α-amylase having an amino acid sequencecorresponding respectively to those α-amylases in (a-d).

(f) Variants of the following parent α-amylases which (i) have one ofthe amino acid sequences shown in corresponding respectively to thoseα-amylases in (a-e), or (ii) displays at least 80% homology with one ormore of said amino acid sequences, and/or displays immunologicalcross-reactivity with an antibody raised against an α-amylase having oneof said amino acid sequences, and/or is encoded by a DNA sequence whichhybridizes with the same probe as a DNA sequence encoding an α-amylasehaving one of said amino acid sequence; in which variants:

1. at least one amino acid residue of said parent α-amylase has beendeleted; and/or

2. at least one amino acid residue of said parent α-amylase has beenreplaced by a different amino acid residue; and/or

3. at least one amino acid residue has been inserted relative to saidparent α-amylase;

said variant having an α-amylase activity and exhibiting at least one ofthe following properties relative to said parent α-amylase: increasedthermostability, increased stability towards oxidation, reduced Ca iondependency, increased stability and/or α-amylolytic activity at neutralto relatively high pH values, increased α-amylolytic activity atrelatively high temperature and increase or decrease of the isoelectricpoint (pI) so as to better match the pI value for α-amylase variant tothe pH of the medium.

Said variants are described in the patent application PCT/DK96/00056.

Other amylases suitable herein include, for example, α-amylasesdescribed in GB 1,296,839 to Novo; RAPIDASE®, InternationalBio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® from Novo isespecially useful. Engineering of enzymes for improved stability, e.g.,oxidative stability, is known. See, for example J. Biological Chem.,Vol. 260, No. 11, June 1985, pp. 6518-6521. Certain preferredembodiments of the present compositions can make use of amylases havingimproved stability in detergents such as automatic dishwashing types,especially improved oxidative stability as measured against areference-point of TERMAMYL® in commercial use in 1993. These preferredamylases herein share the characteristic of being “stability-enhanced”amylases, characterized, at a minimum, by a measurable improvement inone or more of: oxidative stability, e.g., to hydrogenperoxide/tetraacetylethylenediamine in buffered solution at pH 9-10;thermal stability, e.g., at common wash temperatures such as about 60°C.; or alkaline stability, e.g., at a pH from about 8 to about 11,measured versus the above-identified reference-point amylase. Stabilitycan be measured using any of the art-disclosed technical tests. See, forexample, references disclosed in WO 9402597. Stability-enhanced amylasescan be obtained from Novo or from Genencor International. One class ofhighly preferred amylases herein have the commonality of being derivedusing site-directed mutagenesis from one or more of the Bacillusamylases, especially the Bacillus α-amylases, regardless of whether one,two or multiple amylase strains are the immediate precursors. Oxidativestability-enhanced amylases vs. the above-identified reference amylaseare preferred for use, especially in bleaching, more preferably oxygenbleaching, as distinct from chlorine bleaching, detergent compositionsherein. Such preferred amylases include (a) an amylase according to thehereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994, as furtherillustrated by a mutant in which substitution is made, using alanine orthreonine, preferably threonine, of the methionine residue located inposition 197 of the B. licheniformis alpha-amylase, known as TERMAMYL®,or the homologous position variation of a similar parent amylase, suchas B. amyloliquefaciens, B. subtilis, or B. stearothermophilus; (b)stability-enhanced amylases as described by Genencor International in apaper entitled “Oxidatively Resistant alpha-Amylases” presented at the207th American Chemical Society National Meeting, Mar. 13-17 1994, by C.Mitchinson. Therein it was noted that bleaches in automatic dishwashingdetergents inactivate alpha-amylases but that improved oxidativestability amylases have been made by Genencor from B. licheniformisNCIB8061. Methionine (Met) was identified as the most likely residue tobe modified. Met was substituted, one at a time, in positions 8, 15,197, 256, 304, 366 and 438 leading to specific mutants, particularlyimportant being M197L and M197T with the M197T variant being the moststable expressed variant. Stability was measured in CASCADE® andSUNLIGHT®; (c) particularly preferred amylases herein include amylasevariants having additional modification in the immediate parent asdescribed in WO 9510603 A and are available from the assignee, Novo, asDURAMYL®. Other particularly preferred oxidative stability enhancedamylase include those described in WO 9418314 to Genencor Internationaland WO 9402597 to Novo. Any other oxidative stability-enhanced amylasecan be used, for example as derived by site-directed mutagenesis fromknown chimeric, hybrid or simple mutant parent forms of availableamylases. Other preferred enzyme modifications are accessible. See WO9509909 A to Novo.

Bleach Catalysts—The present invention compositions and methods utilizemetal-containing bleach catalysts that are effective for use in ADDcompositions. Preferred are manganese and cobalt-containing bleachcatalysts.

One type of metal-containing bleach catalyst is a catalyst systemcomprising a transition metal cation of defined bleach catalyticactivity, such as copper, iron, titanium, ruthenium tungsten,molybdenum, or manganese cations, an auxiliary metal cation havinglittle or no bleach catalytic activity, such as zinc or aluminumcations, and a sequestrate having defined stability constants for thecatalytic and auxiliary metal cations, particularlyethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Suchcatalysts are disclosed in U.S. Pat. No. 4,430,243.

Other types of bleach catalysts include the manganese-based complexesdisclosed in U.S. Pat. Nos. 5,246,621 and 5,244,594. Preferred examplesof theses catalysts include Mn^(IV)₂(u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂-(PF₆)₂ (“MnTACN”),Mn^(III)₂(u-O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂-(ClO₄)₂,Mn^(IV) ₄(u-O)₆(1,4,7-triazacyclononane)₄-(ClO₄)₂, Mn^(III)Mn^(IV)₄(u-O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂-(ClO₄)₃, andmixtures thereof. See also European patent application publication no.549,272. Other ligands suitable for use herein include1,5,9-trimethyl-1,5,9-triazacyclododecane,2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, andmixtures thereof.

The bleach catalysts useful in automatic dishwashing compositions andconcentrated powder detergent compositions may also be selected asappropriate for the present invention. For examples of suitable bleachcatalysts see U.S. Pat. Nos. 4,246,612 and 5,227,084.

Other bleach catalysts are described, for example, in European patentapplication, publication no. 408,131 (cobalt complex catalysts),European patent applications, publication nos. 384,503, and 306,089(metallo-porphyrin catalysts), U.S. Pat. No. 4,728,455(manganese/multidentate ligand catalyst), U.S. Pat. No. 4,711,748 andEuropean patent application, publication no. 224,952, (absorbedmanganese on aluminosilicate catalyst), U.S. Pat. No. 4,601,845(aluminosilicate support with manganese and zinc or magnesium salt),U.S. Pat. No. 4,626,373 (manganese/ligand catalyst), U.S. Pat. No.4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019(cobalt chelant catalyst) Canadian 866,191 (transition metal-containingsalts), U.S. Pat. No. 4,430,243 (chelants with manganese cations andnon-catalytic metal cations), and U.S. Pat. No. 4,728,455 (manganesegluconate catalysts).

Preferred are cobalt catalysts which have the formula:

[Co(NH₃)_(n)(M′)_(m)]Y_(y)

wherein n is an integer from 3 to 5 (preferably 4 or 5; most preferably5); M′ is a labile coordinating moiety, preferably selected from thegroup consisting of chlorine, bromine, hydroxide, water, and (when m isgreater than 1) combinations thereof; m is an integer from 1 to 3(preferably 1 or 2; most preferably 1); m+n=6; and Y is an appropriatelyselected counteranion present in a number y, which is an integer from 1to 3 (preferably 2 to 3; most preferably 2 when Y is a −1 chargedanion), to obtain a charge-balanced salt.

The preferred cobalt catalyst of this type useful herein are cobaltpentaamine chloride salts having the formula [Co(NH₃)₅Cl]Y_(y), andespecially [Co(NH₃)₅Cl]Cl₂.

More preferred are the present invention compositions which utilizecobalt (III) bleach catalysts having the formula:

[Co(NH₃)_(n)(M)_(m)(B)_(b)]T_(y)

wherein cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5);M is one or more ligands coordinated to the cobalt by one site; m is 0,1 or 2 (preferably 1); B is a ligand coordinated to the cobalt by twosites; b is 0 or 1 (preferably 0), and when b=0, then m+n=6, and whenb=1, then m=0 and n=4; and T is one or more appropriately selectedcounteranions present in a number y, where y is an integer to obtain acharge-balanced salt (preferably y is 1 to 3; most preferably 2 when Tis a −1 charged anion); and wherein further said catalyst has a basehydrolysis rate constant of less than 0.23 M⁻¹ s⁻¹ (25° C.).

Preferred T are selected from the group consisting of chloride, iodide,I₃ ⁻, formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate,carbonate, bromide, PF₆ ⁻, BF₄ ⁻, B(Ph)₄ ⁻, phosphate, phosphite,silicate, tosylate, methanesulfonate, and combinations thereof.Optionally, T can be protonated if more than one anionic group exists inT, e.g., HPO₄ ²⁻, HCO₃ ⁻, H₂PO₄ ⁻, etc. Further, T may be selected fromthe group consisting of non-traditional inorganic anions such as anionicsurfactants (e.g., linear alkylbenzene sulfonates (LAS), alkyl sulfates(AS), alkylethoxysulfonates (AES), etc.) and/or anionic polymers (e.g.,polyacrylates, polymethacrylates, etc.).

The M moieties include, but are not limited to, for example, F⁻, SO₄ ⁻²,NCS⁻, SCN⁻, S₂O₃ ⁻², NH₃, PO₄ ³⁻, and carboxylates (which preferably aremono-carboxylates, but more than one carboxylate may be present in themoiety as long as the binding to the cobalt is by only one carboxylateper moiety, in which case the other carboxylate in the M moiety may beprotonated or in its salt form). Optionally, M can be protonated if morethan one anionic group exists in M (e.g., HPO₄ ²⁻, HCO₃ ⁻, H₂PO₄ ⁻,HOC(O)CH₂C(O)O—, etc.) Preferred M moieties are substituted andunsubstituted C₁-C₃₀ carboxylic acids having the formulas:

RC(O)O—

wherein R is preferably selected from the group consisting of hydrogenand C₁-C₃₀ (preferably C₁-C₁₈) unsubstituted and substituted alkyl,C₆-C₃₀ (preferably C₆-C₁₈) unsubstituted and substituted aryl, andC₃-C₃₀ (preferably C₅-C₁₈) unsubstituted and substituted heteroaryl,wherein substituents are selected from the group consisting of —NR′₃,—NR′₄ ⁺, —C(O)OR′, —OR′, —C(O)NR′₂, wherein R′ is selected from thegroup consisting of hydrogen and C₁-C₆ moieties. Such substituted Rtherefore include the moieties —(CH₂)_(n)OH and —(CH₂)_(n)NR′₄ ⁺,wherein n is an integer from 1 to about 16, preferably from about 2 toabout 10, and most preferably from about 2 to about 5.

Most preferred M are carboxylic acids having the formula above wherein Ris selected from the group consisting of hydrogen, methyl, ethyl,propyl, straight or branched C₄-C₁₂ alkyl, and benzyl. Most preferred Ris methyl. Preferred carboxylic acid M moieties include formic, benzoic,octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic,adipic, phthalic, 2-ethylhexanoic, naphthenoic, oleic, palmitic,triflate, tartrate, stearic, butyric, citric, acrylic, aspartic,fumaric, lauric, linoleic, lactic, malic, and especially acetic acid.

The B moieties include carbonate, di- and higher carboxylates (e.g.,oxalate, malonate, malic, succinate, maleate), picolinic acid, and alphaand beta amino acids (e.g., glycine, alanine, beta-alanine,phenylalanine).

Cobalt bleach catalysts useful herein are known, being described forexample along with their base hydrolysis rates, in M. L. Tobe, “BaseHydrolysis of Transition-Metal Complexes”, Adv. Inorg. Bioinorg. Mech.,(1983), 2, pages 1-94. For example, Table 1 at page 17, provides thebase hydrolysis rates (designated therein as k_(OH)) for cobaltpentaamine catalysts complexed with oxalate (k_(OH)=2.5×10⁻⁴ M⁻¹ s⁻¹(25° C.)), NCS⁻ (k_(OH)=5.0×10⁻⁴ M⁻¹ s⁻¹ (25° C.)), formate(k_(OH)=5.8×10⁻⁴ M⁻¹ s⁻¹ (25° C.)), and acetate (k_(OH)=9.6×10⁻⁴ M⁻¹ s⁻¹(25° C.)). The most preferred cobalt catalyst useful herein are cobaltpentaamine acetate salts having the formula [Co(NH₃)₅OAc]T_(y), whereinOAc represents an acetate moiety, and especially cobalt pentaamineacetate chloride, [Co(NH₃)₅OAc]Cl₂; as well as [Co(NH₃)₅OAc](OAc)₂;[Co(NH₃)₅OAc](PF₆)₂; [Co(NH₃)₅OAc](SO₄); [Co(NH₃)₅OAc](BF₄)₂; and[Co(NH₃)₅OAc](NO₃)₂.

Cobalt catalysts according to the present invention made be producedaccording to the synthetic routes disclosed in U.S. Pat. Nos. 5,559,261,5,581,005, and 5,597,936, the disclosures of which are hereinincorporated by reference.

These catalysts may be coprocessed with adjunct materials so as toreduce the color impact if desired for the aesthetics of the product, orto be included in enzyme-containing particles as exemplifiedhereinafter, or the compositions may be manufactured to contain catalyst“speckles”.

As a practical matter, and not by way of limitation, the cleaningcompositions and cleaning processes herein can be adjusted to provide onthe order of at least one part per hundred million of the active bleachcatalyst species in the aqueous washing medium, and will preferablyprovide from about 0.01 ppm to about 25 ppm, more preferably from about0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm toabout 5 ppm, of the bleach catalyst species in the wash liquor. In orderto obtain such levels the compositions herein will comprise from about0.0005% to about 0.2%, more preferably from about 0.004% to about 0.08%,of bleach catalyst by weight of the cleaning compositions.

Preferred bleach catalysts, along with methods of there use can beadditionally found in U.S. Pat. Nos. 5,705,464, 5,804,542, 5,798,326,5,703,030 and 5,599,781, all of which are incorporated herein byreference.

Conventional Cleaning Agents

These conventional cleaning agents are preferably present in thecleaning compositions of the present invention. Suitable conventionalcleaning agents include builders, surfactants, enzymes other thanamylase, bleach activators, bleach boosters, bleaches, alkalinitysources, colorants, perfume, lime soap dispersants, polymeric dyetransfer inhibiting agents, antibacterial agent, crystal growthinhibitors, photobleaches, heavy metal ion sequestrants, anti-tarnishingagents, anti-microbial agents, anti-oxidants, anti-redeposition agents,soil release polymers, electrolytes, pH modifiers, thickeners,abrasives, divalent metal ions, metal ion salts, enzyme stabilizers,corrosion inhibitors, diamines, suds stabilizing polymers, solvents,process aids, fabric softening agents, optical brighteners, hydrotropes.and mixtures thereof.

Detergent Builders

The present invention may include an optional builder in the productcomposition. The level of detergent salt/builder can vary widelydepending upon the end use of the composition and its desired physicalform. When present, the compositions will typically comprise at leastabout 1% detergent builder and more typically from about 10% to about80%, even more typically from about 15% to about 50% by weight, of thedetergent builder. Lower or higher levels, however, are not meant to beexcluded.

Inorganic or P-containing detergent builders include, but are notlimited to, the alkali metal, ammonium and alkanolammonium salts ofpolyphosphates (exemplified by the tripolyphosphates, pyrophosphates,and glassy polymeric meta-phosphates), phosphonates, phytic acid,silicates, carbonates (including bicarbonates and sesquicarbonates),sulphates, and aluminosilicates. However, non-phosphate salts arerequired in some locales. Importantly, the compositions herein functionsurprisingly well even in the presence of the so-called “weak” builders(as compared with phosphates) such as citrate, or in the so-called“underbuilt” situation that may occur with zeolite or layered silicatebuilders.

Examples of silicate builders are the alkali metal silicates,particularly those having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1and layered silicates, such as the layered sodium silicates described inU.S. Pat. No. 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 isthe trademark for a crystalline layered silicate marketed by Hoechst(commonly abbreviated herein as “SKS-6”). Unlike zeolite builders, theNa SKS-6 silicate builder does not contain aluminum. NaSKS-6 has thedelta-Na2SiO5 morphology form of layered silicate. It can be prepared bymethods such as those described in German DE-A-3,417,649 andDE-A-3,742,043. SKS-6 is a highly preferred layered silicate for useherein, but other such layered silicates, such as those having thegeneral formula NaMSixO2x+1.yH2O wherein M is sodium or hydrogen, x is anumber from 1.9 to 4, preferably 2, and y is a number from 0 to 20,preferably 0 can be used herein. Various other layered silicates fromHoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta andgamma forms. As noted above, the delta-Na2SiO5 (NaSKS-6 form) is mostpreferred for use herein. Other silicates may also be useful such as forexample magnesium silicate, which can serve as a crispening agent ingranular formulations, as a stabilizing agent for oxygen bleaches, andas a component of suds control systems.

Examples of carbonate salts as builders are the alkaline earth andalkali metal carbonates as disclosed in German Patent Application No.2,321,001 published on Nov. 15, 1973.

Aluminosilicate builders may also be added to the present invention as adetergent salt. Aluminosilicate builders are of great importance in mostcurrently marketed heavy duty granular detergent compositions.Aluminosilicate builders include those having the empirical formula:

M_(z)(zAlO₂)_(y) ]—xH₂O

wherein z and y are integers of at least 6, the molar ratio of z to y isin the range from 1.0 to about 0.5, and x is an integer from about 15 toabout 264.

Useful aluminosilicate ion exchange materials are commerciallyavailable. These aluminosilicates can be crystalline or amorphous instructure and can be naturally-occurring aluminosilicates orsynthetically derived. A method for producing aluminosilicate ionexchange materials is disclosed in U.S. Pat. No. 3,985,669, Krummel, etal, issued Oct. 12, 1976. Preferred synthetic crystallinealuminosilicate ion exchange materials useful herein are available underthe designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. Inan especially preferred embodiment, the crystalline aluminosilicate ionexchange material has the formula:

Na₁₂[(AlO₂)₁₂(SiO₂)₁₂ ]—xH₂O

wherein x is from about 20 to about 30, especially about 27. Thismaterial is known as Zeolite A. Dehydrated zeolites (x=0-10) may also beused herein. Preferably, the aluminosilicate has a particle size ofabout 0.1-10 microns in diameter.

Organic detergent builders suitable for the purposes of the presentinvention include, but are not restricted to, a wide variety ofpolycarboxylate compounds. As used herein, “polycarboxylate” refers tocompounds having a plurality of carboxylate groups, preferably at least3 carboxylates. Polycarboxylate builder can generally be added to thecomposition in acid form, but can also be added in the form of aneutralized salt. When utilized in salt form, alkali metals, such assodium, potassium, and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are a variety of categoriesof useful materials. One important category of polycarboxylate buildersencompasses the ether polycarboxylates, including oxydisuccinate, asdisclosed in Berg, U.S. Pat. No. 3,128,287, issued Apr. 7, 1964, andLamberti et al, U.S. Pat. No. 3,635,830, issued Jan. 18, 1972. See also“TMS/TDS” builders of U.S. Pat. No. 4,663,071, issued to Bush et al, onMay 5, 1987. Suitable ether polycarboxylates also include cycliccompounds, particularly alicyclic compounds, such as those described inU.S. Pat. Nos. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detergency builders include the etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ether, 1,3,5-trihydroxy benzene-2,4,6-trisulphonic acid,and carboxymethyloxysuccinic acid, the various alkali metal, ammoniumand substituted ammonium salts of polyacetic acids such asethylenediamine tetraacetic acid and nitrilotriacetic acid, as well aspolycarboxylates such as mellitic acid, succinic acid, oxydisuccinicacid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof(particularly sodium salt), are polycarboxylate builders of particularimportance. Oxydisuccinates are also especially useful in suchcompositions and combinations.

Also suitable in the detergent compositions of the present invention arethe 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Pat. No. 4,566,984, Bush, issued Jan. 28, 1986. Usefulsuccinic acid builders include the C5-C20 alkyl and alkenyl succinicacids and salts thereof. A particularly preferred compound of this typeis dodecenylsuccinic acid. Specific examples of succinate buildersinclude: laurylsuccinate, myristylsuccinate, palmitylsuccinate,2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.Laurylsuccinates are the preferred builders of this group, and aredescribed in European Patent Application 86200690.5/0,200,263, publishedNov. 5, 1986.

Other suitable polycarboxylates are disclosed in U.S. Pat. No.4,144,226, Crutchfield et al, issued Mar. 13, 1979 and in U.S. Pat. No.3,308,067, Diehl, issued Mar. 7, 1967. See also Diehl U.S. Pat. No.3,723,322.

Fatty acids, e.g., C12-C18 monocarboxylic acids, can also beincorporated into the compositions alone, or in combination with theaforesaid builders, especially citrate and/or the succinate builders, toprovide additional builder activity. Such use of fatty acids willgenerally result in a diminution of sudsing, which should be taken intoaccount by the formulator.

Surfactants

Surfactants may be included in the compositions of the present inventionas ultrasonic cleaning agent. The surfactant may comprise from about0.01%, to about 99.9%, by weight of the composition depending upon theparticular surfactants used and the effects desired. More typical levelscomprise from about 0.1% to about 80%, even more preferably from about0.5% to about 60%, by weight of the composition. Examples of suitablesurfactants can be found in McCutcheon's EMULSIFIERS AND DETERGENTS,North American Edition, 1997, McCutcheon Division, MC PublishingCompany, in U.S. Pat. No. 3,929,678, Dec. 30, 1975 Laughlin, et al, andU.S. Pat. No. 4,259,217, Mar. 31, 1981, Murphy; in the series“Surfactant Science”, Marcel Dekker, Inc., New York and Basel; in“Handbook of Surfactants”, M. R. Porter, Chapman and Hall, 2nd Ed.,1994; in “Surfactants in Consumer Products”, Ed. J. Falbe,Springer-Verlag, 1987 and “Surface Active Agents and Detergents” (Vol. Iand II by Schwartz, Perry and Berch) all of which are incorporatedhereinbefore by reference.

The detersive surfactant can be nonionic, anionic, ampholytic,zwitterionic, or cationic. Mixtures of these surfactants can also beused. Preferred detergent compositions comprise anionic detersivesurfactants or mixtures of anionic surfactants with other surfactants,especially nonionic surfactants and/or amphoteric surfactants.

Nonlimiting examples of surfactants useful herein include theconventional C11-C18 alkyl benzene sulfonates and primary, secondary andrandom alkyl sulfates, the C10-C18 alkyl alkoxy sulfates, the C10-C18alkyl polyglycosides and their corresponding sulfated polyglycosides,C12-C18 alpha-sulfonated fatty acid esters, C12-C18 alkyl and alkylphenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy),C12-C18 betaines and sulfobetaines (“sultaines”), C10-C18 amine oxides,C₆ to C₁₈ branched or linear alkyl sulfates, C₆ to C₈ branched or linearalkyl benzene sulfonates, C₆ to C₁₈ branched or linear alkyl alkoxysulfates, and mixtures thereof. and the like. Other conventional usefulsurfactants are listed in standard texts.

Anionic Surfactants

The anionic surfactants useful in the present invention are preferablyselected from the group consisting of, linear alkylbenzene sulfonate,alpha olefin sulfonate, paraffin sulfonates, alkyl ester sulfonates,alkyl sulfates, alkyl alkoxy sulfate, alkyl sulfonates, alkyl alkoxycarboxylate, alkyl alkoxylated sulfates, sarcosinates, taurinates, andmixtures thereof, more preferably C₆ to C₁₈ branched or linear alkylsulfates, C₆ to C₁₈ branched or linear alkyl benzene sulfonates, C₆ toC₁₈ branched or linear alkyl alkoxy sulfates, and mixtures thereof. Aneffective amount, typically from about 0.5% to about 90%, preferablyabout 5% to about 60%, more preferably from about 10 to about 30%, byweight of anionic detersive surfactant can be used in the presentinvention.

Alkyl sulfate surfactants are another type of anionic surfactant ofimportance for use herein. In addition to providing excellent overallcleaning ability when used in combination with polyhydroxy fatty acidamides (see below), including good grease/oil cleaning over a wide rangeof temperatures, wash concentrations, and wash times, dissolution ofalkyl sulfates can be obtained, as well as improved formulability inliquid detergent formulations are water soluble salts or acids of theformula ROSO₃M wherein R preferably is a C₁₀-C₂₄ hydrocarbyl, preferablyan alkyl or hydroxyalkyl having a C₁₀-C₂₀ alkyl component, morepreferably a C₁₂-C₁₈ alkyl or hydroxyalkyl, and M is H or a cation,e.g., an alkali (Group IA) metal cation (e.g., sodium, potassium,lithium), substituted or unsubstituted ammonium cations such as methyl-,dimethyl-, and trimethyl ammonium and quaternary ammonium cations, e.g.,tetramethyl-ammonium and dimethyl piperdinium, and cations derived fromalkanolamines such as ethanolamine, diethanolamine, triethanolamine, andmixtures thereof, and the like. Typically, alkyl chains of C₁₂₋₁₆ arepreferred for lower wash temperatures (e.g., below about 50° C.) andC₁₆₋₁₈ alkyl chains are preferred for higher wash temperatures (e.g.,above about 50° C.).

Alkyl alkoxylated sulfate surfactants are another category of usefulanionic surfactant. These surfactants are water soluble salts or acidstypically of the formula RO(A)_(m)SO₃M wherein R is an unsubstitutedC₁₀-C₂₄ alkyl or hydroxyalkyl group having a C₁₀-C₂₄ alkyl component,preferably a C₁₂-C₂₀ alkyl or hydroxyalkyl, more preferably C₁₂-C₁₈alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater thanzero, typically between about 0.5 and about 6, more preferably betweenabout 0.5 and about 3, and M is H or a cation which can be, for example,a metal cation (e.g., sodium, potassium, lithium, etc.), ammonium orsubstituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkylpropoxylated sulfates are contemplated herein. Specific examples ofsubstituted ammonium cations include methyl-, dimethyl-,trimethyl-ammonium and quaternary ammonium cations, such astetramethyl-ammonium, dimethyl piperidinium and cations derived fromalkanolamines, e.g. monoethanolamine, diethanolamine, andtriethanolamine, and mixtures thereof. Exemplary surfactants are C₁₂-C₁₈alkyl polyethoxylate (1.0) sulfate, C₁₂-C₁₈ alkyl polyethoxylate (2.25)sulfate, C₁₂-C₁₈ alkyl polyethoxylate (3.0) sulfate, and C₁₂-C₁₈ alkylpolyethoxylate (4.0) sulfate wherein M is conveniently selected fromsodium and potassium. Surfactants for use herein can be made fromnatural or synthetic alcohol feedstocks. Chain lengths represent averagehydrocarbon distributions, including branching.

Examples of suitable anionic surfactants are given in “Surface ActiveAgents and Detergents” (Vol. I and II by Schwartz, Perry and Berch). Avariety of such surfactants are also generally disclosed in U.S. Pat.No. 3,929,678, issued Dec. 30, 1975 to Laughlin, et al. at Column 23,line 58 through Column 29, line 23.

Another possible surfactant are the so-called Dianionics. These aresurfactants which have at least two anionic groups present on thesurfactant molecule. Some suitable dianionic surfactants are furtherdescribed in copending U.S. Ser. Nos. 60/020,503, 60/020,772,60/020,928, 60/020,832 and 60/020,773 all filed on Jun. 28, 1996, andNos. 60/023,539, 60/023493, 60/023,540 and 60/023,527 filed on Aug. 8,1996, the disclosures of which are incorporated herein by reference.Other conventional useful surfactants are listed in standard texts.

Nonionic Surfactants—One particularly preferred surfactants are nonionicsurfactants. Nonionic surfactants may be present in amounts from 0.01%to about 40% by weight, preferably from about 0.1% to about 30%, andmost preferably from about 0.25% to about 20%.

Particularly preferred in the present invention include mixed nonionicsurfactants. While a wide range of nonionic surfactants may be selectedfrom for purposes of the mixed nonionic surfactant systems useful in thepresent invention compositions, it is preferred that the nonionicsurfactants comprise both a low cloud point surfactant as represented bythe ether capped poly(oxyalkylated) alcohol surfactant and high cloudpoint nonionic surfactant(s) as described as follows. “Cloud point”, asused herein, is a well known property of nonionic surfactants which isthe result of the surfactant becoming less soluble with increasingtemperature, the temperature at which the appearance of a second phaseis observable is referred to as the “cloud point” (See Kirk Othmer, pp.360-362, hereinbefore).

As used herein, a “low cloud point” nonionic surfactant is defined as anonionic surfactant system ingredient having a cloud point of less than30° C., preferably less than about 20° C., and most preferably less thanabout 10° C. and is represented by the ether-capped poly(oxyalkylated)alcohols as described herein.

Of course, other low-cloud point surfactants may be included inconjunction with the ether-capped poly(oxyalkylated) surfactants. Suchoptional low-cloud point surfactants include nonionic alkoxylatedsurfactants, especially ethoxylates derived from primary alcohol, andpolyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverseblock polymers. Also, such low cloud point nonionic surfactants include,for example, ethoxylated-propoxylated alcohol (e.g., Olin Corporation'sPoly-Tergent® SLF18) and epoxy-capped poly(oxyalkylated) alcohols (e.g.,Olin Corporation's Poly-Tergent® SLF18B series of nonionics, asdescribed, for example, in WO 94/22800, published Oct. 13, 1994 by OlinCorporation). These nonionic surfactants can optionally containpropylene oxide in an amount up to about 15% by weight. Other preferrednonionic surfactants can be prepared by the processes described in U.S.Pat. No. 4,223,163, issued Sep. 16, 1980, Builloty, incorporated hereinby reference.

Optional low cloud point nonionic surfactants additionally comprise apolyoxyethylene, polyoxypropylene block polymeric compound. Blockpolyoxyethylene-polyoxypropylene polymeric compounds include those basedon ethylene glycol, propylene glycol, glycerol, trimethylolpropane andethylenediamine as initiator reactive hydrogen compound. Certain of theblock polymer surfactant compounds designated PLURONIC®, REVERSEDPLURONIC®, and TETRONIC® by the BASF-Wyandotte Corp., Wyandotte, Mich.,are suitable in ADD compositions of the invention. Preferred examplesinclude REVERSED PLURONIC® 25R2 and TETRONIC® 702, Such surfactants aretypically useful herein as low cloud point nonionic surfactants.

As used herein, a “high cloud point” nonionic surfactant is defined as anonionic surfactant system ingredient having a cloud point of greaterthan 40° C., preferably greater than about 50° C., and more preferablygreater than about 60° C. Preferably the nonionic surfactant systemcomprises an ethoxylated surfactant derived from the reaction of amonohydroxy alcohol or alkylphenol containing from about 8 to about 20carbon atoms, with from about 6 to about 15 moles of ethylene oxide permole of alcohol or alkyl phenol on an average basis. Such high cloudpoint nonionic surfactants include, for example, Tergitol 15S9 (suppliedby Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), andNeodol 91-8 (supplied by Shell).

It is also preferred for purposes of the present invention that the highcloud point nonionic surfactant further have a hydrophile-lipophilebalance (“HLB”; see Kirk Othmer hereinbefore) value within the range offrom about 9 to about 15, preferably 11 to 15. Such materials include,for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).

Another preferred high cloud point nonionic surfactant is derived from astraight or preferably branched chain or secondary fatty alcoholcontaining from about 6 to about 20 carbon atoms (C6-C20 alcohol),including secondary alcohols and branched chain primary alcohols.Preferably, high cloud point nonionic surfactants are branched orsecondary alcohol ethoxylates, more preferably mixed C9/11 or C11/15branched alcohol ethoxylates, condensed with an average of from about 6to about 15 moles, preferably from about 6 to about 12 moles, and mostpreferably from about 6 to about 9 moles of ethylene oxide per mole ofalcohol. Preferably the ethoxylated nonionic surfactant so derived has anarrow ethoxylate distribution relative to the average.

The preferred nonionic surfactant systems useful herein are mixed highcloud point and low cloud point nonionic surfactants combined in aweight ratio preferably within the range of from about 10:1 to about1:10.

Another preferred LFNIs are the endcapped alkyl alkoxylate surfactants.Suitable endcapped alkyl alkoxylate surfactant are the epoxy-cappedpoly(oxyalkylated) alcohols represented by the formula:

R₁O[CH₂CH(CH₃)O]_(x)[CH₂CH₂O]_(y)[CH₂CH(OH)R₂]  (I)

wherein R₁ is a linear or branched, aliphatic hydrocarbon radical havingfrom 4 to 18 carbon atoms; R₂ is a linear or branched aliphatichydrocarbon radical having from 2 to 26 carbon atoms; x is an integerhaving an average value of from 0.5 to 1.5, more preferably 1; and y isan integer having a value of at least 15, more preferably at least 20.

Preferably, the surfactant of formula I, at least 10 carbon atoms in theterminal epoxide unit [CH₂CH(OH)R₂]. Suitable surfactants of formula I,according to the present invention, are Olin Corporation's POLY-TERGENT®SLF-18B nonionic surfactants, as described, for example, in WO 94/22800,published Oct. 13, 1994 by Olin Corporation.

One preferred ether-capped poly(oxyalkylated) alcohols has the formula:

R¹O[CH₂CH(R³)O]_(x)[CH₂]_(k)CH(OH)[CH₂]_(j)OR²

wherein R¹ and R² are linear or branched, saturated or unsaturated,aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbonatoms; R³ is H, or a linear aliphatic hydrocarbon radical having from 1to 4 carbon atoms; x is an integer having an average value from 1 to 30,wherein when x is 2 or greater R³ may be the same or different and k andj are integers having an average value of from 1 to 12, and morepreferably 1 to 5.

R¹ and R² are preferably linear or branched, saturated or unsaturated,aliphatic or aromatic hydrocarbon radicals having from 6 to 22 carbonatoms with 8 to 18 carbon atoms being most preferred. H or a linearaliphatic hydrocarbon radical having from 1 to 2 carbon atoms is mostpreferred for R³. Preferably, x is an integer having an average value offrom 1 to 20, more preferably from 6 to 15.

As described above, when, in the preferred embodiments, and x is greaterthan 2, R³ may be the same or different. That is, R³ may vary betweenany of the alklyeneoxy units as described above. For instance, if x is3, R³ may be selected to form ethlyeneoxy(EO) or propyleneoxy(PO) andmay vary in order of (EO)(PO)(EO), (EO)(EO)(PO); (EO)(EO)(EO);(PO)(EO)(PO); (PO)(PO)(EO) and (PO)(PO)(PO). Of course, the integerthree is chosen for example only and the variation may be much largerwith a higher integer value for x and include, for example, multiple(EO) units and a much small number of (PO) units.

Particularly preferred surfactants as described above include those thathave a low cloud point of less than 20° C. These low cloud pointsurfactants may then be employed in conjunction with a high cloud pointsurfactant as described in detail below for superior grease cleaningbenefits.

Most preferred ether-capped poly(oxyalkylated) alcohol surfactants arethose wherein k is 1 and j is 1 so that the surfactants have theformula:

 R¹O[CH₂CH(R³)O]_(x)CH₂CH(OH)CH₂OR²

where R¹, R² and R³ are defined as above and x is an integer with anaverage value of from 1 to 30, preferably from 1 to 20, and even morepreferably from 6 to 18. Most preferred are surfactants wherein R¹ andR² range from 9 to 14, R³ is H forming ethyleneoxy and x ranges from 6to 15.

The ether-capped poly(oxyalkylated) alcohol surfactants comprise threegeneral components, namely a linear or branched alcohol, an alkyleneoxide and an alkyl ether end cap. The alkyl ether end cap and thealcohol serve as a hydrophobic, oil-soluble portion of the moleculewhile the alkylene oxide group forms the hydrophilic, water-solubleportion of the molecule.

These surfactants exhibit significant improvements in spotting andfilming characteristics and removal of greasy soils, when used inconjunction with high cloud point surfactants, relative to conventionalsurfactants.

Another suitable class of nonionic surfactants comprises sugar derivedsurfactants such as the polyhydroxy fatty acid amides of the formula:

wherein: R¹ is H, C₁-C₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl,or a mixture thereof, preferably C₁-C₄ alkyl, more preferably C₁ or C₂alkyl, most preferably C₁ alkyl (i.e., methyl); and R² is a C₅-C₃₁hydrocarbyl, preferably straight chain C₇-C₁₉ alkyl or alkenyl, morepreferably straight chain C₉-C₁₇ alkyl or alkenyl, most preferablystraight chain C₁₁-C₁₅ alkyl or alkenyl, or mixtures thereof; and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivative(preferably ethoxylated or propoxylated) thereof. Z preferably will bederived from a reducing sugar in a reductive amination reaction; morepreferably Z will be a glycityl. Suitable reducing sugars includeglucose, fructose, maltose, lactose, galactose, mannose, and xylose. Asraw materials, high dextrose corn syrup, high fructose corn syrup, andhigh maltose corn syrup can be utilized as well as the individual sugarslisted above. These corn syrups may yield a mix of sugar components forZ. It should be understood that it is by no means intended to excludeother suitable raw materials. Z preferably will be selected from thegroup consisting of —CH₂—(CHOH)_(n)—CH₂OH,—CH(CH₂OH)—(CHOH)_(n−1)—CH₂OH, —CH₂—(CHOH)₂(CHOR′)(CHOH)—CH₂OH, andalkoxylated derivatives thereof, where n is an integer from 3 to 5,inclusive, and R′ is H or a cyclic or aliphatic monosaccharide. Mostpreferred are glycityls wherein n is 4, particularly —CH₂—(CHOH)₄—CH₂OH.

R′ can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl,N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.

R²—CO—N< can be, for example, cocamide, stearamide, oleamide, lauramide,myristamide, capricamide, palmitamide, tallowamide, etc.

Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl,1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl,1-deoxymaltotriotityl, etc.

Methods for making polyhydroxy fatty acid amides are known in the art.In general, they can be made by reacting an alkyl amine with a reducingsugar in a reductive amination reaction to form a corresponding N-alkylpolyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with afatty aliphatic ester or triglyceride in a condensation/amidation stepto form the N-alkyl, N-polyhydroxy fatty acid amide product. Processesfor making compositions containing polyhydroxy fatty acid amides aredisclosed, for example, in G.B. Patent Specification 809,060, publishedFeb. 18, 1959, by Thomas Hedley & Co., Ltd., U.S. Pat. No. 2,965,576,issued Dec. 20, 1960 to E. R. Wilson, and U.S. Pat. No. 2,703,798,Anthony M. Schwartz, issued Mar. 8, 1955, and U.S. Pat. No. 1,985,424,issued Dec. 25, 1934 to Piggott, each of which is incorporated herein byreference.

The preferred alkylpolyglycosides have the formula

R²O(C_(n)H_(2n)O)_(t)(glycosyl)_(x)

wherein R² is selected from the group consisting of alkyl, alkyl-phenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from about 10 to about 18, preferably from about 12to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 toabout 10, preferably 0; and x is from about 1.3 to about 10, preferablyfrom about 1.3 to about 3, most preferably from about 1.3 to about 2.7.The glycosyl is preferably derived from glucose. To prepare thesecompounds, the alcohol or alkylpolyethoxy alcohol is formed first andthen reacted with glucose, or a source of glucose, to form the glucoside(attachment at the 1-position). The additional glycosyl units can thenbe attached between their 1-position and the preceding glycosyl units2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position.

These and other nonionic surfactants are well known in the art, beingdescribed in more detail in Kirk Othmer's Encyclopedia of ChemicalTechnology, 3rd Ed., Vol. 22, pp. 360-379, “Surfactants and DetersiveSystems”, incorporated by reference herein. Further suitable nonionicdetergent surfactants are generally disclosed in U.S. Pat. No.3,929,678, Laughlin et al., issued Dec. 30, 1975, at column 13, line 14through column 16, line 6, incorporated herein by reference.

Cationic Surfactants

Cationic surfactants suitable for use in the compositions of the presentinvention include those having a long-chain hydrocarbyl group. Examplesof such cationic co-surfactants include the ammonium co-surfactants suchas alkyldimethylammonium halogenides, and those co-surfactants havingthe formula:

[R²(OR³)_(y)][R⁴(OR³)_(y)]₂R⁵N⁺X⁻

wherein R² is an alkyl or alkyl benzyl group having from 8 to 18 carbonatoms in the alkyl chain, each R³ is selected from the group consistingof —CH₂CH₂—, —CH₂CH(CH₃)—, —CH₂CH(CH₂OH)—, —CH₂CH₂CH₂—, and mixturesthereof; each R⁴ is selected from the group consisting of C₁-C₄ alkyl,C₁-C₄ hydroxyalkyl, benzyl ring structures formed by joining the two R⁴groups, —CH₂CHOH—CHOHCOR⁶CHOHCH₂OH wherein R⁶ is any hexose or hexosepolymer having a molecular weight less than about 1000, and hydrogenwhen y is not 0; R⁵ is the same as R⁴ or is an alkyl chain wherein thetotal number of carbon atoms of R² plus R⁵ is not more than about 18;each y is from 0 to about 10 and the sum of the y values is from 0 toabout 15; and X is any compatible anion.

Examples of other suitable cationic surfactants are described infollowing documents, all of which are incorporated by reference hereinin their entirety: M.C. Publishing Co., McCutcheon's, Detergents &Emulsifiers, (North American edition 1997); Schwartz, et al., SurfaceActive Agents, Their Chemistry and Technology, New York: IntersciencePublishers, 1949; U.S. Pat. Nos. 3,155,591; 3,929,678; 3,959,4614,387,090 and 4,228,044.

Examples of suitable cationic surfactants are those corresponding to thegeneral formula:

wherein R₁, R₂, R₃, and R₄ are independently selected from an aliphaticgroup of from 1 to about 22 carbon atoms or an aromatic, alkoxy,polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl grouphaving up to about 22 carbon atoms; and X is a salt-forming anion suchas those selected from halogen, (e.g. chloride, bromide), acetate,citrate, lactate, glycolate, phosphate nitrate, sulfate, andalkylsulfate radicals. The aliphatic groups can contain, in addition tocarbon and hydrogen atoms, ether linkages, and other groups such asamino groups. The longer chain aliphatic groups, e.g., those of about 12carbons, or higher, can be saturated or unsaturated. Preferred is whenR₁, R₂, R₃, and R₄ are independently selected from C1 to about C22alkyl. Especially preferred are cationic materials containing two longalkyl chains and two short alkyl chains or those containing one longalkyl chain and three short alkyl chains. The long alkyl chains in thecompounds described in the previous sentence have from about 12 to about22 carbon atoms, preferably from about 16 to about 22 carbon atoms, andthe short alkyl chains in the compounds described in the previoussentence have from 1 to about 3 carbon atoms, preferably from 1 to about2 carbon atoms.

Suitable levels of cationic detersive surfactant herein, when present,are from about 0.1% to about 20%, preferably from about 1% to about 15%,although much higher levels, e.g., up to about 30% or more, may beuseful especially in nonionic:cationic (i.e., limited or anionic-free)formulations.

Other Surfactants

Amphoteric or zwitterionic detersive surfactants when present areusually useful at levels in the range from about 0.1% to about 20% byweight of the detergent composition. Often levels will be limited toabout 5% or less, especially when the amphoteric is costly.

Suitable amphoteric surfactants include the amine oxides correspondingto the formula:

RR′R″N→O

wherein R is a primary alkyl group containing 6-24 carbons, preferably10-18 carbons, and wherein R′ and R″ are, each, independently, an alkylgroup containing 1 to 6 carbon atoms. The arrow in the formula is aconventional representation of a semi-polar bond.

Amine oxides are semi-polar surfactants and include water-soluble amineoxides containing one alkyl moiety of from about 10 to about 18 carbonatoms and 2 moieties selected from the group consisting of alkyl groupsand hydroxyalkyl groups containing from about 1 to about 3 carbon atoms;water-soluble phosphine oxides containing one alkyl moiety of from about10 to about 18 carbon atoms and 2 moieties selected from the groupconsisting of alkyl groups and hydroxyalkyl groups containing from about1 to about 3 carbon atoms; and water-soluble sulfoxides containing onealkyl moiety of from about 10 to about 18 carbon atoms and a moietyselected from the group consisting of alkyl and hydroxyalkyl moieties offrom about 1 to about 3 carbon atoms.

Preferred amine oxide surfactants having the formula

wherein R³ is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixturesthereof containing from about 8 to about 22 carbon atoms; R⁴ is analkylene or hydroxyalkylene group containing from about 2 to about 3carbon atoms or mixtures thereof; x is from 0 to about 3; and each R⁵ isan alkyl or hydroxyalkyl group containing from about 1 to about 3 carbonatoms or a polyethylene oxide group containing from about 1 to about 3ethylene oxide groups. The R⁵ groups can be attached to each other,e.g., through an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include C₁₀-C₁₈ alkyldimethyl amine oxides and C₈-C₁₂ alkoxy ethyl dihydroxy ethyl amineoxides. Preferably the amine oxide is present in the composition in aneffective amount, more preferably from about 0.1% to about 20%, evenmore preferably about 0.1% to about 15%, even more preferably still fromabout 0.5% to about 10%, by weight.

Some suitable zwitterionic surfactants which can be used herein comprisethe betaine and betaine-like surfactants wherein the molecule containsboth basic and acidic groups which form an inner salt giving themolecule both cationic and anionic hydrophilic groups over a broad rangeof pH values. Some common examples of these s are described in U.S. Pat.Nos. 2,082,275, 2,702,279 and 2,255,082, incorporated herein byreference. One of the preferred zwitterionic compounds have the formula

wherein R1 is an alkyl radical containing from 8 to 22 carbon atoms, R2and R3 contain from 1 to 3 carbon atoms, R4 is an alkylene chaincontaining from 1 to 3 carbon atoms, X is selected from the groupconsisting of hydrogen and a hydroxyl radical, Y is selected from thegroup consisting of carboxyl and sulfonyl radicals and wherein the sumof R1, R2 and R3 radicals is from 14 to 24 carbon atoms.

Zwitterionic surfactants, as mentioned hereinbefore, contain both acationic group and an anionic group and are in substantial electricalneutrality where the number of anionic charges and cationic charges onthe surfactant molecule are substantially the same. Zwitterionics, whichtypically contain both a quaternary ammonium group and an anionic groupselected from sulfonate and carboxylate groups are desirable since theymaintain their amphoteric character over most of the pH range ofinterest for cleaning hard surfaces. The sulfonate group is thepreferred anionic group.

Antimicrobial agents—an antimicrobial agent is a compound or substancethat kills microorganisms or prevents or inhibits their growth andreproduction. A properly selected antimicrobial agent maintainsstability under use and storage conditions (pH, temperature, light,etc.), for a required length of time. A desirable property of theantimicrobial agent is that it is safe and nontoxic in handling,formulation and use, is environmentally acceptable and cost effective.Classes of antimicrobial agents include, but are not limited to,chlorophenols, aldehydes, biguanides, antibiotics and biologicallyactive salts. Some preferable antimicrobial agent in the antimicrobialis bronopol, chlorhexidine diacetate, TRICOSAN.TM., hexetidineorparachlorometaxylenol (PCMX). More preferably, the antimicrobial agentis TRICOSAN.TM, chlorhexidine diacetate or hexetidine.

The antimicrobial agent, when used, is present in a microbiocidallyeffective amount, more preferably an from about 0.01% to about 10.0%,more preferably from about 0.1% to about 8.0%, even more preferably fromabout 0.5% to about 2.0%, by weight of c the composition.

Bleaching Agents

Hydrogen peroxide sources are described in detail in the hereinincorporated Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed(1992, John Wiley & Sons), Vol. 4, pp. 271-300 “Bleaching Agents(Survey)”, and include the various forms of sodium perborate and sodiumpercarbonate, including various coated and modified forms. An “effectiveamount” of a source of hydrogen peroxide is any amount capable ofmeasurably improving stain removal (especially of tea stains) fromsoiled dishware compared to a hydrogen peroxide source-free compositionwhen the soiled dishware is washed by the consumer in a domesticautomatic dishwasher in the presence of alkali.

More generally a source of hydrogen peroxide herein is any convenientcompound or mixture which under consumer use conditions provides aneffective amount of hydrogen peroxide. Levels may vary widely and areusually in the range from about 0.1% to about 70%, more typically fromabout 0.5% to about 30%, by weight of the compositions herein.

The preferred source of hydrogen peroxide used herein can be anyconvenient source, including hydrogen peroxide itself. For example,perborate, e.g., sodium perborate (any hydrate but preferably the mono-or tetra-hydrate), sodium carbonate peroxyhydrate or equivalentpercarbonate salts, sodium pyrophosphate peroxyhydrate, ureaperoxyhydrate, or sodium peroxide can be used herein. Also useful aresources of available oxygen such as persulfate bleach (e.g., OXONE,manufactured by DuPont). Sodium perborate monohydrate and sodiumpercarbonate are particularly preferred. Mixtures of any convenienthydrogen peroxide sources can also be used.

A preferred percarbonate bleach comprises dry particles having anaverage particle size in the range from about 500 micrometers to about1,000 micrometers, not more than about 10% by weight of said particlesbeing smaller than about 200 micrometers and not more than about 10% byweight of said particles being larger than about 1,250 micrometers.Optionally, the percarbonate can be coated with a silicate, borate orwater-soluble surfactants. Percarbonate is available from variouscommercial sources such as FMC, Solvay and Tokai Denka.

While not preferred for the compositions of the present invention whichcomprise detersive enzymes, the present invention compositions may alsocomprise as the bleaching agent a chlorine-type bleaching material. Suchagents are well known in the art, and include for example sodiumdichloroisocyanurate (“NaDCC”).

Organic Peroxides especially Diacyl Peroxides

These are extensively illustrated in Kirk Othmer, Encyclopedia ofChemical Technology, Vol. 17, John Wiley and Sons, 1982 at pages 27-90and especially at pages 63-72, all incorporated herein by reference. Ifa diacyl peroxide is used, it will preferably be one which exertsminimal adverse impact on spotting/filming. Preferred diacyl peroxidesinclude dibenzoyl peroxide.

Bleach Activators

Preferably, when composition contains a peroxygen bleach component thecomposition is formulated with an activator (peracid precursor).Preferred activators are selected from the group consisting oftetraacetyl ethylene diamine (TAED), benzoylcaprolactam (BzCL),4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam,benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS),phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C₁₀-OBS),benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (C₈-OBS),perhydrolyzable esters and mixtures thereof, most preferablybenzoylcaprolactam and benzoylvalerolactam. Particularly preferredbleach activators in the pH range from about 8 to about 9.5 are thoseselected having an OBS or VL leaving group.

Preferred bleach activators are those described in U.S. Pat. No.5,130,045, Mitchell et al, and U.S. Pat. No. 4,412,934, Chung et al, andcopending patent applications U.S. Ser. Nos. 08/064,624, 08/064,623,08/064,621, 08/064,562, 08/064,564, 08/082,270 and copending applicationto M. Burns, A. D. Willey, R. T. Hartshom, C. K. Ghosh, entitled“Bleaching Compounds Comprising Peroxyacid Activators Used With Enzymes”and having U.S. Ser. No. 08/133,691 (P&G Case 4890R), all of which areincorporated herein by reference.

The mole ratio of peroxygen bleaching compound (as AvO) to bleachactivator in the present invention generally ranges from at least 1:1,preferably from about 20:1 to about 1:1, more preferably from about 10:1to about 3:1.

Quaternary substituted bleach activators may also be included. Thepresent detergent compositions preferably comprise a quaternarysubstituted bleach activator (QSBA) or a quaternary substituted peracid(QSP); more preferably, the former. Preferred QSBA structures arefurther described in copending U.S. Ser. Nos. 08/298,903, 08/298,650,08/298,906 and 08/298,904 filed Aug. 31, 1994, incorporated herein byreference.

Levels of bleach activators herein may vary widely, e.g., from about0.01% to about 90%, by weight of the composition, although lower levels,e.g., more preferably from about 0.1% to about 30%, even more preferablyfrom about 0.1% to about 20%, even more preferably from about 0.5% toabout 10%, even more still preferably from about 1% to about 8%, byweight of the composition are more typically used.

Preferred hydrophilic bleach activators include N,N,N′N′-tetraacetylethylene diamine (TAED) or any of its close relatives including thetriacetyl or other unsymmetrical derivatives. TAED and the acetylatedcarbohydrates such as glucose pentaacetate and tetraacetyl xylose arepreferred hydrophilic bleach activators. Depending on the application,acetyl triethyl citrate, a liquid, also has some utility, as does phenylbenzoate.

Preferred hydrophobic bleach activators include substituted amide typesdescribed in detail hereinafter, such as activators related to NAPAA,and activators related to certain imidoperacid bleaches, for example asdescribed in U.S. Pat. No. 5,061,807, issued Oct. 29, 1991 and assignedto Hoechst Aktiengesellschaft of Frankfurt, Germany.

Other suitable bleach activators include sodium-4-benzoyloxy benzenesulfonate (SBOBS); sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate;sodium-4-methyl-3-benzoyloxy benzoate (SPCC); trimethyl ammoniumtoluyloxy-benzene sulfonate; or sodium 3,5,5-trimethylhexanoyloxybenzene sulfonate (STHOBS).

Bleach activators may be used in any amount, typically up to 20%,preferably from 0.1-10% by weight, of the composition, though higherlevels, 40% or more, are acceptable, for example in highly concentratedbleach additive product forms or forms intended for appliance automateddosing.

Highly preferred bleach activators useful herein are amide-substitutedand have either of the formulae:

or mixtures thereof, wherein R¹ is alkyl, aryl, or alkaryl containingfrom about 1 to about 14 carbon atoms including both hydrophilic types(short R¹) and hydrophobic types (R¹ is especially from 6, preferablyabout 8, to about 12), R² is alkylene, arylene or alkarylene containingfrom about 1 to about 14 carbon atoms, R⁵ is H, or an alkyl, aryl, oralkaryl containing from about 1 to about 10 carbon atoms, and L is aleaving group which is herein before defined.

Preferred bleach activators also include those of the above generalformula wherein L is selected from the group consisting of:

wherein R³ is as defined above and Y is —SO3⁻M⁺ or —CO2⁻M⁺ wherein M isas defined above.

Preferred examples of bleach activators of the above formulae include:

(6-octanamidocaproyl)oxybenzenesulfonate,

(6-nonanamidocaproyl)oxybenzenesulfonate,

(6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof.

Other useful activators, disclosed in U.S. Pat. No. 4,966,723, arebenzoxazin-type, such as a C₆H₄ ring to which is fused in the1,2-positions a moiety —C(O)OC(R¹)═N—. A highly preferred activator ofthe benzoxazin-type is:

Acyl lactam activators are very useful herein, especially the acylcaprolactams (see for example WO 94-28102 A) and acyl valerolactams (seeU.S. Pat. No. 5,503,639) of the formulae:

wherein R⁶ is H, alkyl, aryl, alkoxyaryl, an alkaryl group containingfrom 1 to about 12 carbon atoms, or substituted phenyl containing fromabout 6 to about 18 carbons. See also U.S. Pat. No. 4,545,784 whichdiscloses acyl caprolactams, including benzoyl caprolactam adsorbed intosodium perborate.

Nonlimiting examples of additional activators useful herein are to befound in U.S. Pat. Nos. 4,915,854, 4,412,934 and 4,634,551.

Additional activators useful herein include those of U.S. Pat. No.5,545,349. Examples include esters of an organic acid and ethyleneglycol, diethylene glycol or glycerin, or the acid imide of an organicacid and ethylenediamine; wherein the organic acid is selected frommethoxyacetic acid, 2-methoxypropionic acid, p-methoxybenzoic acid,ethoxyacetic acid, 2-ethoxypropionic acid, p-ethoxybenzoic acid,propoxyacetic acid, 2-propoxypropionic acid, p-propoxybenzoic acid,butoxyacetic acid, 2-butoxypropionic acid, p-butoxybenzoic acid,2-methoxyethoxyacetic acid, 2-methoxy-1-methylethoxyacetic acid,2-methoxy-2-methylethoxyacetic acid, 2-ethoxyethoxyacetic acid,2-(2-ethoxyethoxy)propionic acid, p-(2-ethoxyethoxy)benzoic acid,2-ethoxy-1-methylethoxyacetic acid, 2-ethoxy-2-methylethoxyacetic acid,2-propoxyethoxyacetic acid, 2-propoxy-1-methylethoxyaceticacid,2-propoxy-2-methylethoxyacetic acid, 2-butoxyethoxyacetic acid,2-butoxy-1-methylethoxyacetic acid, 2-butoxy-2-methylethoxyacetic acid,2-(2-methoxyethoxy)ethoxyacetic acid,2-(2-methoxy-1-methylethoxy)ethoxyacetic acid,2-(2-methoxy-2-methylethoxy)ethoxyacetic acid and2-(2-ethoxyethoxy)ethoxyacetic acid.

Useful herein as oxygen bleaches are the inorganic peroxides such asNa₂O₂, superoxides such as KO₂, organic hydroperoxides such as cumenehydroperoxide and t-butyl hydroperoxide, and the inorganic peroxoacidsand their salts such as the peroxosulfuric acid salts, especially thepotassium salts of peroxodisulfuric acid and, more preferably, ofperoxomonosulfuric acid including the commercial triple-salt form soldas OXONE by DuPont and also any equivalent commercially available formssuch as CUROX from Akzo or CAROAT from Degussa. Certain organicperoxides, such as dibenzoyl peroxide, may be useful, especially asadditives rather than as primary oxygen bleach.

Mixed oxygen bleach systems are generally useful, as are mixtures of anyoxygen bleaches with the known bleach activators, organic catalysts,enzymatic catalysts and mixtures thereof; moreover such mixtures mayfurther include brighteners, photobleaches and dye transfer inhibitorsof types well-known in the art.

Other useful peracids and bleach activators herein are in the family ofimidoperacids and imido bleach activators. These includephthaloylimidoperoxycaproic acid and related arylimido-substituted andacyloxynitrogen derivatives. For listings of such compounds,preparations and their incorporation into laundry compositions includingboth granules and liquids, See U.S. Pat. Nos. 5,487,818; 5,470,988,5,466,825; 5,419,846; 5,415,796; 5,391,324; 5,328,634; 5,310,934;5,279,757; 5,246,620; 5,245,075; 5,294,362; 5,423,998; 5,208,340;5,132,431 and 5,087385.

Additional bleach activators are those described in U.S. Pat. No.5,130,045, Mitchell et al, and U.S. Pat. No. 4,412,934, Chung et al, andcopending patent applications U.S. Ser. Nos. 08/064,624, 08/064,623,08/064,621, 08/064,562, 08/064,564, 08/082,270 and copending applicationto M. Burns, A. D. Willey, R. T. Hartshorn, C. K. Ghosh, entitled“Bleaching Compounds Comprising Peroxyacid Activators Used With Enzymes”and having U.S. Ser. No. 08/133,691 (P&G Case 4890R), all of which areincorporated herein by reference.

Quaternary substituted bleach activators may also be included. Thepresent detergent compositions preferably comprise a quatemarysubstituted bleach activator (QSBA) or a quaternary substituted peracid(QSP); more preferably, the former. Preferred QSBA structures arefurther described in copending U.S. Pat. Nos. 5,460,747, 5,584,888 and5,578,136, incorporated herein by reference.

Useful diperoxyacids include, for example, 1,12-diperoxydodecanedioicacid (DPDA); 1,9-diperoxyazelaic acid; diperoxybrassilic acid;diperoxysebasic acid and diperoxyisophthalic acid;2-decyldiperoxybutane-1,4-dioic acid; and 4,4′-sulphonylbisperoxybenzoicacid. Owing to structures in which two relatively hydrophilic groups aredisposed at the ends of the molecule, diperoxyacids have sometimes beenclassified separately from the hydrophilic and hydrophobic monoperacids,for example as “hydrotropic”. Some of the diperacids are hydrophobic ina quite literal sense, especially when they have a long-chain, moietyseparating the peroxyacid moieties.

It is stressed that if any bleach activators are used then they arelimited to ones which cause minimal, preferably no damage to the rubbercomponents in a domestic bleaching process.

Reducing Bleaches

Another class of useful bleaches are the so called reducing bleaches.These are reductants which “reduce”, in the electrochemical sense,instead of oxidize as conventional bleaches do. Examples of suitablereducing bleaches can be found in These are extensively illustrated inKirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wileyand Sons, 1982.

Enzymatic Sources of Hydrogen Peroxide

On a different track from the oxygen bleaching agents illustratedhereinabove, another suitable hydrogen peroxide generating system is acombination of a C₁-C₄ alkanol oxidase and a C₁-C₄ alkanol, especially acombination of methanol oxidase (MOX) and ethanol. Such combinations aredisclosed in WO 94/03003. Other enzymatic materials related tobleaching, such as peroxidases, haloperoxidases, oxidases, superoxidedismutases, catalases and their enhancers or, more commonly, inhibitors,may be used as optional ingredients in the instant compositions.

Oxygen Transfer Agents and Precursors

Also useful herein are any of the known organic bleach catalysts, oxygentransfer agents or precursors therefor. These include the compoundsthemselves and/or their precursors, for example any suitable ketone forproduction of dioxiranes and/or any of the hetero-atom containinganalogs of dioxirane precursors or dioxiranes, such as sulfoniminesR¹R²C═NSO₂R³, see EP 446 982 A, published 1991 and sulfonyloxaziridines,for example:

see EP 446,981 A, published 1991. Preferred examples of such materialsinclude hydrophilic or hydrophobic ketones, used especially inconjunction with monoperoxysulfates to produce dioxiranes in situ,and/or the imines described in U.S. Pat. No. 5,576,282 and referencesdescribed therein. Oxygen bleaches preferably used in conjunction withsuch oxygen transfer agents or precursors include percarboxylic acidsand salts, percarbonic acids and salts, peroxymonosulfuric acid andsalts, and mixtures thereof. See also U.S. Pat. Nos. 5,360,568;5,360,569; and 5,370,826. In a highly preferred embodiment, theinvention relates to a detergent composition which incorporates atransition-metal bleach catalyst in accordance with the invention, andorganic bleach catalyst such as one named hereinabove, a primary oxidantsuch as a hydrogen peroxide source, a hydrophilic bleach activator, andat least one additional detergent, hard-surface cleaner or automaticdishwashing adjunct. Preferred among such compositions are those whichfurther include a precursor for a hydrophobic oxygen bleach such.

Composition pH

Compositions of the invention will have a pH range of from about 2 toabout 13, preferably, pH is alkaline, more preferably from about 7 toabout 12.5, more preferably from about 8 to about 12, even morepreferably from about 9 to about 11.5. If a composition with a pHgreater than 7 is to be more effective, it preferably should contain abuffering agent capable of providing a generally more alkaline pH in thecomposition and in dilute solutions, i.e., about 0.1% to 0.4% by weightaqueous solution, of the composition. The pKa value of this bufferingagent should be about 0.5 to 1.0 pH units below the desired pH value ofthe composition (determined as described above). Preferably, the pKa ofthe buffering agent should be from about 7 to about 10. Under theseconditions the buffering agent most effectively controls the pH whileusing the least amount thereof.

The buffering agent may be an active detergent in its own right, or itmay be a low molecular weight, organic or inorganic material that isused in this composition solely for maintaining an alkaline pH.Preferred buffering agents for compositions of this invention arenitrogen-containing materials. Some examples are amino acids such aslysine or lower alcohol amines like mono-, di-, and tri-ethanolamine.Other preferred nitrogen-containing buffering agents areTri(hydroxymethyl)amino methane (HOCH2)3CNH3(TRIS),2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-propanol,2-amino-2-methyl-1,3-propanol, disodium glutamate, N-methyldiethanolamide, 1,3-diamino-propanolN,N′-tetra-methyl-1,3-diamino-2-propanol, N,N-bis(2-hydroxyethyl)glycine(bicine) and N-tris (hydroxymethyl)methyl glycine (tricine). Mixtures ofany of the above are also acceptable. Useful inorganicbuffers/alkalinity sources include the alkali metal carbonates andalkali metal phosphates, e.g., sodium carbonate, sodium polyphosphate.For additional buffers see McCutcheon's EMULSIFIERS AND DETERGENTS,North American Edition, 1997, McCutcheon Division, MC Publishing CompanyKirk and WO 95/07971 both of which are incorporated herein by reference.

The buffering agent, if used, is present in the compositions of theinvention herein at a level of from about 0.1% to 15%, preferably fromabout 1% to 10%, most preferably from about 2% to 8%, by weight of thecomposition.

Diamines—It is preferred that the diamines used in the present inventionare substantially free from impurities. That is, by “substantially free”it is meant that the diamines are over 95% pure, i.e., preferably 97%,more preferably 99%, still more preferably 99.5%, free of impurities.Examples of impurities which may be present in commercially supplieddiamines include 2-Methyl-1,3-diaminobutane and alkylhydropyrimidine.Further, it is believed that the diamines should be free of oxidationreactants to avoid diamine degradation and ammonia formation.

It is further preferred that the compositions of the present inventionbe “malodor” free. That is, that the odor of the headspace does notgenerate a negative olfactory response from the consumer. This can beachieved in many ways, including the use of perfumes to mask anyundesirable odors, the use of stabilizers, such as antioxidants,chelants etc., and/or the use of diamines which are substantially freeof impurities. It is believed, without wanting to being limited bytheory, that it is the impurities present in the diamines that are thecause of most of the malodors in the compositions of the presentinvention. These impurities can form during the preparation and storageof the diamines. They can also form during the preparation and storageof the inventive composition. The use of stabilizers such asantioxidants and chelants inhibit and/or prevent the formation of theseimpurities in the composition from the time of preparation to ultimateuse by the consumer and beyond. Hence, it is most preferred to remove,suppress and/or prevent the formation of these malodors by the additionof perfumes, stabilizers and/or the use of diamines which aresubstantially free from impurities.

Preferred organic diamines are those in which pK1 and pK2 are in therange of about 8.0 to about 11.5, preferably in the range of about 8.4to about 11, even more preferably from about 8.6 to about 10.75.Preferred materials for performance and supply considerations are1,3-bis(methylamine)-cyclohexane, 1,3 propane diamine (pK1=10.5;pK2=8.8), 1,6 hexane diamine (pK1=11; pK2=10), 1,3 pentane diamine(Dytek EP) (pK1=10.5; pK2=8.9), 2-methyl 1,5 pentane diamine (Dytek A)(pK1=11.2; pK2=10.0). Other preferred materials are the primary/primarydiamines with alkylene spacers ranging from C4 to C8. In general, it isbelieved that primary diamines are preferred over secondary and tertiarydiamines.

Definition of pK1 and pK2—As used herein, “pKa1” and “pKa2” arequantities of a type collectively known to those skilled in the art as“pKa.” pKa is used herein in the same manner as is commonly known topeople skilled in the art of chemistry. Values referenced herein can beobtained from literature, such as from “Critical Stability Constants:Volume 2, Amines” by Smith and Martel, Plenum Press, NY and London,1975. Additional information on pKa's can be obtained from relevantcompany literature, such as information supplied by Dupont, a supplierof diamines.

As a working definition herein, the pKa of the diamines is specified inan allaqueous solution at 25° C. and for an ionic strength between 0.1to 0.5 M. The pKa is an equilibrium constant which can change withtemperature and ionic strength; thus, values reported in the literatureare sometimes not in agreement depending on the measurement method andconditions. To eliminate ambiguity, the relevant conditions and/orreferences used for pKa's of this invention are as defined herein or in“Critical Stability Constants: Volume 2, Amines”. One typical method ofmeasurement is the potentiometric titration of the acid with sodiumhydroxide and determination of the pKa by suitable methods as describedand referenced in “The Chemist's Ready Reference Handbook” by Shugar andDean, McGraw Hill, NY, 1990.

It has been determined that substituents and structural modificationsthat lower pK1 and pK2 to below about 8.0 are undesirable and causelosses in performance. This can include substitutions that lead toethoxylated diamines, hydroxy ethyl substituted diamines, diamines withoxygen in the beta (and less so gamma) position to the nitrogen in thespacer group (e.g., Jeffamine EDR 148). In addition, materials based onethylene diamine are unsuitable.

The diamines useful herein can be defined by the following structure:

wherein R₂₋₅ are independently selected from H, methyl, —CH₃CH₂, andethylene oxides; C_(x) and C_(v) are independently selected frommethylene groups or branched alkyl groups where x+y is from about 3 toabout 6; and A is optionally present and is selected from electrondonating or withdrawing moieties chosen to adjust the diamine pKa's tothe desired range. If A is present, then x and y must both be 1 orgreater.

Alternatively the preferred diamines can be those with a molecularweight less than or equal to 400 g/mol. It is preferred that thesediamines have the formula:

wherein each R⁶ is independently selected from the group consisting ofhydrogen, C₁-C₄ linear or branched alkyl, alkyleneoxy having theformula:

—(R⁷O)_(m)R⁸

wherein R⁷ is C₂-C₄ linear or branched alkylene, and mixtures thereof;R⁸ is hydrogen, C₁-C₄ alkyl, and mixtures thereof; m is from 1 to about10; X is a unit selected from:

i) C₃-C₁₀ linear alkylene, C₃-C₁₀ branched alkylene, C₃-C₁₀ cyclicalkylene, C₃-C₁₀ branched cyclic alkylene, an alkyleneoxyalkylene havingthe formula:

—(R⁷O)_(m)R⁷—

 wherein R⁷ and m are the same as defined herein above;

ii) C₃-C₁₀ linear, C₃-C₁₀ branched linear, C₃-C₁₀ cyclic, C₃-C₁₀branched cyclic alkylene, C₆-C₁₀ arylene, wherein said unit comprisesone or more electron donating or electron withdrawing moieties whichprovide said diamine with a pKa greater than about 8; and

iii) mixtures of (i) and (ii) provided said diamine has a pKa of atleast about 8.

Examples of preferred diamines include the following:

Dimethyl aminopropyl amine:

1,6-Hexane Diamine:

1,3 propane diamine—

2-methyl 1,5 pentane diamine—

1,3-pentanediamine, available under the tradename Dytek EP

1-methyl-diaminopropane—

Jeffamine EDR 148—

Isophorone diamine—

1,3-bis(methylamine)-cyclohexane

and mixtures thereof.

Solvents

Optionally, the compositions of the present invention may furthercomprise one or more solvents. These solvents may be used in conjunctionwith an aqueous liquid carrier or they may be used without any aqueousliquid carrier being present. Solvents are broadly defined as compoundsthat are liquid at temperatures of 20° C.-25° C. and which are notconsidered to be surfactants. One of the distinguishing features is thatsolvents tend to exist as discrete entities rather than as broadmixtures of compounds. Some solvents which are useful in the hardsurface cleaning compositions of the present invention contain from 1carbon atom to 35 carbon atoms, and contain contiguous linear, branchedor cyclic hydrocarbon moieties of no more than 8 carbon atoms. Examplesof suitable solvents for the present invention include, methanol,ethanol, propanol, isopropanol, 2-methyl pyrrolidinone, benzyl alcoholand morpholine n-oxide. Preferred among these solvents are methanol andisopropanol.

The compositions used herein may optionally contain an alcohol having ahydrocarbon chain comprising 8 to 18 carbon atoms, preferably 12 to 16.The hydrocarbon chain can be branched or linear, and can be mono, di orpolyalcohols. The compositions used herein can optionally comprise from0.1% to 3% by weight of the total composition of such alcohol, ormixtures thereof, preferably from 0.1% to 1%.

The solvents which can be used herein include all those known to thethose skilled in the art of hard-surfaces cleaner compositions. Suitablesolvents for use herein include ethers and diethers having from 4 to 14carbon atoms, preferably from 6 to 12 carbon atoms, and more preferablyfrom 8 to 10 carbon atoms. Also other suitable solvents are glycols oralkoxylated glycols, alkoxylated aromatic alcohols, aromatic alcohols,aliphatic branched alcohols, alkoxylated aliphatic branched alcohols,alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, C8-C14 alkyland cycloalkyl hydrocarbons and halohydrocarbons, C6-C16 glycol ethersand mixtures thereof.

Suitable glycols which can be used herein are according to the formulaHO—CR1R2-OH wherein R1 and R2 are independently H or a C2-C10 saturatedor unsaturated aliphatic hydrocarbon chain and/or cyclic. Suitableglycols to be used herein are dodecaneglycol and/or propanediol.

Suitable alkoxylated glycols which can be used herein are according tothe formula R—(A)n—R1-OH wherein R is H, OH, a linear saturated orunsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15and more preferably from 2 to 10, wherein R1 is H or a linear saturatedor unsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to15 and more preferably from 2 to 10, and A is an alkoxy group preferablyethoxy, methoxy, and/or propoxy and n is from 1 to 5, preferably 1 to 2.Suitable alkoxylated glycols to be used herein are methoxy octadecanoland/or ethoxyethoxyethanol.

Suitable alkoxylated aromatic alcohols which can be used herein areaccording to the formula R (A)_(n)—OH wherein R is an alkyl substitutedor non-alkyl substituted aryl group of from 1 to 20 carbon atoms,preferably from 2 to 15 and more preferably from 2 to 10, wherein A isan alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is aninteger of from 1 to 5, preferably 1 to 2. Suitable alkoxylated aromaticalcohols are benzoxyethanol and/or benzoxypropanol.

Suitable aromatic alcohols which can be used herein are according to theformula R—OH wherein R is an alkyl substituted or non-alkyl substitutedaryl group of from 1 to 20 carbon atoms, preferably from 1 to 15 andmore preferably from 1 to 10. For example a suitable aromatic alcohol tobe used herein is benzyl alcohol.

Suitable aliphatic branched alcohols which can be used herein areaccording to the formula R—OH wherein R is a branched saturated orunsaturated alkyl group of from 1 to 20 carbon atoms, preferably from 2to 15 and more preferably from 5 to 12. Particularly suitable aliphaticbranched alcohols to be used herein include 2-ethylbutanol and/or2-methylbutanol.

Suitable alkoxylated aliphatic branched alcohols which can be usedherein are according to the formula R (A)_(n)—OH wherein R is a branchedsaturated or unsaturated alkyl group of from 1 to 20 carbon atoms,preferably from 2 to 15 and more preferably from 5 to 12, wherein A isan alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is aninteger of from 1 to 5, preferably 1 to 2. Suitable alkoxylatedaliphatic branched alcohols include 1-methylpropoxyethanol and/or2-methylbutoxyethanol.

Suitable alkoxylated linear C1-C5 alcohols which can be used herein areaccording to the formula R (A)_(n)—OH wherein R is a linear saturated orunsaturated alkyl group of from 1 to 5 carbon atoms, preferably from 2to 4, wherein A is an alkoxy group preferably butoxy, propoxy and/orethoxy, and n is an integer of from 1 to 5, preferably 1 to 2. Suitablealkoxylated aliphatic linear C1-C5 alcohols are butoxy propoxy propanol(n-BPP), butoxyethanol, butoxypropanol, ethoxyethanol or mixturesthereof. Butoxy propoxy propanol is commercially available under thetrade name n-BPP® from Dow chemical.

Suitable linear C1-C5 alcohols which can be used herein are according tothe formula R—OH wherein R is a linear saturated or unsaturated alkylgroup of from 1 to 5 carbon atoms, preferably from 2 to 4. Suitablelinear C1-C5 alcohols are methanol, ethanol, propanol or mixturesthereof.

Other suitable solvents include, but are not limited to, butyl diglycolether (BDGE), butyltriglycol ether, ter amilic alcohol and the like.Particularly preferred solvents which can be used herein are butoxypropoxy propanol, butyl diglycol ether, benzyl alcohol, butoxypropanol,ethanol, methanol, isopropanol and mixtures thereof.

Typically, the compositions used in the methods of the present inventionpreferably comprise up to 20% by weight of the total composition of asolvent or mixtures thereof, more preferably from 0.5% to 10%, even morepreferably from 3% to 10% and even more preferably still from 1% to 8%,by weight.

Other suitable solvents for use herein include propylene glycolderivatives such as n-butoxypropanol or n-butoxypropoxypropanol,water-soluble CARBITOL® solvents or water-soluble CELLOSOLVE® solvents;water-soluble CARBITOL® solvents are compounds of the2-(2-alkoxyethoxy)ethanol class wherein the alkoxy group is derived fromethyl, propyl or butyl; a preferred water-soluble carbitol is2-(2-butoxyethoxy)ethanol also known as butyl carbitol. Water-solubleCELLOSOLVE® solvents are compounds of the 2-alkoxyethoxy ethanol class,with 2-butoxyethoxyethanol being preferred. Other suitable solventsinclude benzyl alcohol, and diols such as 2-ethyl-1,3-hexanediol and2,2,4-trimethyl-1,3-pentanediol and mixtures thereof. Some preferredsolvents for use herein are n-butoxypropoxypropanol, BUTYL CARBITOL® andmixtures thereof.

The solvents can also be selected from the group of compounds comprisingether derivatives of mono-, di-and tri-ethylene glycol, propyleneglycol, butylene glycol ethers, and mixtures thereof. The molecularweights of these solvents are preferably less than 350, more preferablybetween 100 and 300, even more preferably between 115 and 250. Examplesof preferred solvents include, for example, mono-ethylene glycol n-hexylether, mono-propylene glycol n-butyl ether, and tri-propylene glycolmethyl ether. Ethylene glycol and propylene glycol ethers arecommercially available from the Dow Chemical Company under the tradename“Dowanol” and from the Arco Chemical Company under the tradename“Arcosolv”. Other preferred solvents including mono- and di-ethyleneglycol n-hexyl ether are available from the Union Carbide company.

Hydrophobic Solvent

In order to improve cleaning in liquid compositions, one can use ahydrophobic solvent that has cleaning activity. The hydrophobic solventswhich may be employed in the hard surface cleaning compositions hereincan be any of the well-known “degreasing” solvents commonly used in, forexample, the dry cleaning industry, in the hard surface cleaner industryand the metalworking industry.

A useful definition of such solvents can be derived from the solubilityparameters as set forth in “The Hoy,” a publication of Union Carbide,incorporated herein by reference. The most useful parameter appears tobe the hydrogen bonding parameter which is calculated by the formula:${\gamma \quad H} = {\gamma \quad {T\quad\lbrack \frac{a - 1}{a} \rbrack}^{1/2}}$

wherein γH is the hydrogen bonding parameter, a is the aggregationnumber,

(Log α=3.39066 T_(b)/T_(c)−0.15848−Log M)

and

γT is the solubility parameter which is obtained from the formula:${\gamma \quad T} = \lbrack \frac{( {{\Delta \quad H_{25}} - {RT}} )d}{M} \rbrack^{1/2}$

where ΔH₂₅ is the heat of vaporization at 25° C., R is the gas constant(1.987 cal/mole/deg), T is the absolute temperature in °K, T_(b) is theboiling point in °K, T_(c) is the critical temperature in °K, d is thedensity in g/ml, and M is the molecular weight.

For the compositions herein, hydrogen bonding parameters are preferablyless than 7.7, more preferably from 2 to 7, or 7.7, and even morepreferably from 3 to 6. Solvents with lower numbers become increasinglydifficult to solubilize in the compositions and have a greater tendencyto cause a haze on glass. Higher numbers require more solvent to providegood greasy/oily soil cleaning.

Hydrophobic solvents are typically used, when present, at a level offrom 0.5% to 30%, preferably from 2% to 15%, more preferably from 3% to8%. Dilute compositions typically have solvents at a level of from 1% to10%, preferably from 3% to 6%. Concentrated compositions contain from10% to 30%, preferably from 10% to 20% of solvent.

Many of such solvents comprise hydrocarbon or halogenated hydrocarbonmoieties of the alkyl or cycloalkyl type, and have a boiling point wellabove room temperature, i.e., above 20° C.

One highly preferred solvent is limonene, which not only has good greaseremoval but also a pleasant odor properties.

The formulator of compositions of the present type will be guided in theselection of solvent partly by the need to provide good grease-cuttingproperties, and partly by aesthetic considerations. For example,kerosene hydrocarbons function quite well for grease cutting in thepresent compositions, but can be malodorous. Kerosene must beexceptionally clean before it can be used, even in commercialsituations. For home use, where malodors would not be tolerated, theformulator would be more likely to select solvents which have arelatively pleasant odor, or odors which can be reasonably modified byperfuming.

The C₆-C₉ alkyl aromatic solvents, especially the C₆-C₉ alkyl benzenes,preferably octyl benzene, exhibit excellent grease removal propertiesand have a low, pleasant odor. Likewise, the olefin solvents having aboiling point of at least 100° C., especially alpha-olefins, preferably1-decene or 1-dodecene, are excellent grease removal solvents.

Generically, glycol ethers useful herein have the formulaR¹¹O—(R¹²O—)_(m)1H wherein each R¹¹ is an alkyl group which containsfrom 3 to 8 carbon atoms, each R¹² is either ethylene or propylene, andm¹ is a number from 1 to 3. The most preferred glycol ethers areselected from the group consisting of monopropyleneglycolmonopropylether, dipropyleneglycolmonobutyl ether, monopropyleneglycolmonobutylether, ethyleneglycolmonohexyl ether, ethyleneglycolmonobutyl ether,diethyleneglycolmonohexyl ether, monoethyleneglycolmonohexyl ether,monoethyleneglycolmonobutyl ether, and mixtures thereof.

A particularly preferred type of solvent for these hard surface cleanercompositions comprises diols having from 6 to 16 carbon atoms in theirmolecular structure. Preferred diol solvents have a solubility in waterof from 0.1 to 20 g/100 g of water at 20° C. The diol solvents inaddition to good grease cutting ability, impart to the compositions anenhanced ability to remove calcium soap soils from surfaces such asbathtub and shower stall walls. These soils are particularly difficultto remove, especially for compositions which do not contain an abrasive.Other solvents such as benzyl alcohol, n-hexanol, and phthalic acidesters of C₁₋₄ alcohols can also be used.

Solvents such as pine oil, orange terpene, benzyl alcohol, n-hexanol,phthalic acid esters of C₁₋₄ alcohols, butoxy propanol, Butyl Carbitol®and 1(2-n-butoxy-1-methylethoxy)propane-2-ol (also called butoxy propoxypropanol or dipropylene glycol monobutyl ether), hexyl diglycol (HexylCarbitol®), butyl triglycol, diols such as2,2,4-trimethyl-1,3-pentanediol, and mixtures thereof, can be used. Thebutoxy-propanol solvent should have no more than 20%, preferably no morethan 10%, more preferably no more than 7%, of the secondary isomer inwhich the butoxy group is attached to the secondary atom of the propanolfor improved odor.

The level of hydrophobic solvent is preferably, when present, from 1% to15%, more preferably from 2% to 12%, even more preferably from 5% to10%.

Hydrotropes

The compositions used in the methods of the present invention mayoptionally comprise one or more materials which are hydrotropes.Hydrotropes suitable for use in the compositions herein include theC₁-C₃ alkyl aryl sulfonates, C₆-C₁₂ alkanols, C₁-C₆ carboxylic sulfatesand sulfonates, urea, C₁-C₆ hydrocarboxylates, C₁-C₄ carboxylates, C₂-C₄organic diacids and mixtures of these hydrotrope materials. Thecomposition of the present invention preferably comprises from 0.5% to8%, by weight of the liquid detergent composition of a hydrotropeselected from alkali metal and calcium xylene and toluene sulfonates.

Suitable C₁-C₃ alkyl aryl sulfonates include sodium, potassium, calciumand ammonium xylene sulfonates; sodium, potassium, calcium and ammoniumtoluene sulfonates; sodium, potassium, calcium and ammonium cumenesulfonates; and sodium, potassium, calcium and ammonium substituted orunsubstituted naphthalene sulfonates and mixtures thereof.

Suitable C₁-C₈ carboxylic sulfate or sulfonate salts are any watersoluble salts or organic compounds comprising 1 to 8 carbon atoms(exclusive of substituent groups), which are substituted with sulfate orsulfonate and have at least one carboxylic group. The substitutedorganic compound may be cyclic, acylic or aromatic, i.e. benzenederivatives. Preferred alkyl compounds have from 1 to 4 carbon atomssubstituted with sulfate or sulfonate and have from 1 to 2 carboxylicgroups. Examples of this type of hydrotrope include sulfosuccinatesalts, sulfophthalic salts, sulfoacetic salts, m-sulfobenzoic acid saltsand diester sulfosuccinates, preferably the sodium or potassium salts asdisclosed in U.S. Pat. No. 3,915,903.

Suitable C₁-C₄ hydrocarboxylates and C₁-C₄ carboxylates for use hereininclude acetates and propionates and citrates. Suitable C₂-C₄ diacidsfor use herein include succinic, glutaric and adipic acids.

Other compounds which deliver hydrotropic effects suitable for useherein as a hydrotrope include C₆-C₁₂ alkanols and urea.

Preferred hydrotropes for use herein are sodium, potassium, calcium andammonium cumene sulfonate; sodium, potassium, calcium and ammoniumxylene sulfonate; sodium, potassium, calcium and ammonium toluenesulfonate and mixtures thereof. Most preferred are sodium cumenesulfonate and calcium xylene sulfonate and mixtures thereof. Thesepreferred hydrotrope materials can be present in the composition to theextent of from 0.5% to 8% by weight.

Polymeric Suds Stabilizers

The compositions of the present invention may also contain a polymericsuds stabilizer. The compositions preferably comprise at least aneffective amount of the polymeric suds stabilizers described herein,more preferably from about 0.01% to about 10%, even more preferably fromabout 0.05% to about 5%, even more preferably still preferably fromabout 0.1% to about 2% by weight, of said composition. What is meantherein by “an effective amount polymeric suds stabilizers ” is that thesuds volume and suds duration produced by the presently describedcompositions are sustained for an increased amount of time relative to acomposition which does not comprise one or more of the polymeric sudsstabilizer described herein. Additionally, the polymeric suds stabilizercan be present as the free base or as a salt. Typical counter ionsinclude, citrate, maleate, sulfate, chloride, etc.

One preferred polymeric suds stabilizer are polymers comprising at leastone monomeric unit of the formula:

wherein each of R¹, R² and R³ are independently selected from the groupconsisting of hydrogen, C₁ to C₆ alkyl, and mixtures thereof, preferablyhydrogen, C₁ to C₃ alkyl, more preferably, hydrogen or methyl. L isselected from the group consisting of a bond, O, NR⁶, SR⁷R⁸ and mixturesthereof, preferably, O, NR⁶, wherein R⁶ is selected from the groupconsisting of hydrogen, C₁ to C₈ alkyl and mixtures thereof, preferably,hydrogen, C₁ to C₃, and mixtures thereof, more preferably hydrogen,methyl; each of R⁷ and R⁸ are independently hydrogen, O, C₁ to C₈ alkyland mixtures thereof, preferably, hydrogen, C₁ to C₃, and mixturesthereof, more preferably hydrogen or methyl. By “O”, an oxygen linkedvia a double bond is meant, such as a carbonyl group. Furthermore thismeans that when either or both R⁷R⁸ is “O”, SR⁷R⁸ can have the followingstructures:

Alternatively, SR⁷R⁸ form a heterocyclic ring containing from 4 to 7carbon atoms, optionally containing additional hetero atoms andoptionally substituted. For example SR⁷R⁸ can be:

However, it is preferred that SR⁷R⁸, when present, is not a heterocycle.

When L is a bond it means that there is a direct link, or a bond,between the carbonyl carbon atom to Z, when z is not zero. For example:

When L is a bond and z is zero, it means L is a bond from the carbonylatom to A. For example:

Z is selected from the group consisting of: —(CH₂)—, (CH₂—CH═CH)—,—(CH₂—CHOH)—, (CH₂—CHNR⁶), —(CH₂—CHR¹⁴—O)— and mixtures thereof,preferably —(CH₂)—. R¹⁴ is selected from the group consisting ofhydrogen, C₁ to C₆ alkyl and mixtures thereof, preferably hydrogen,methyl, ethyl and mixtures thereof, z is an integer selected from about0 to about 12, preferably about 2 to about 10, more preferably about 2to about 6.

A is NR⁴R⁵. Wherein each of R⁴ and R⁵ are is independently selected fromthe group consisting of hydrogen, C₁-C₈ linear or branched alkyl,alkyleneoxy having the formula:

—(R¹⁰O)_(y)R¹¹

wherein R¹⁰ is C₂-C₄ linear or branched alkylene, and mixtures thereof;R¹¹ is hydrogen, C₁-C₄ alkyl, and mixtures thereof; y is from 1 to about10. Preferably R⁴ and R⁵ are independently, hydrogen, C₁ to C₄ alkyl.Alternatively, NR⁴R⁵ can form a heterocyclic ring containing from 4 to 7carbon atoms, optionally containing additional hetero atoms, optionallyfused to a benzene ring, and optionally substituted by C₁ to C₈hydrocarbyl. Examples of suitable heterocycles, both substituted andunsubstituted, are indolyl, isoindolinyl imidazolyl, imidazolinyl,piperidinyl pyrazolyl, pyrazolinyl, pyridinyl, piperazinyl,pyrrolidinyl, pyrrolidinyl, guanidino, amidino, quinidinyl, thiazolinyl,morpholine and mixtures thereof, with morpholino and piperazinyl beingpreferred. Furthermore the polymeric suds stabilizer has a molecularweight of from about 1,000 to about 2,000,000 preferably from about5,000 to about 1,000,000, more preferably from about 10,000 to about750,000, more preferably from about 20,000 to about 500,000, even morepreferably from about 35,000 to about 300,000 daltons. The molecularweight of the polymeric suds boosters, can be determined viaconventional gel permeation chromatography.

While, it is preferred that the polymeric suds stabilizers be selectedfrom homopolymer, copolymers and terpolymers, other polymers (ormultimers) of the at least one monomeric unit, the polymeric sudsstabilizers can also be envisioned via polymerization of the at leastone monomeric unit with a wider selection of monomers. That is, all thepolymeric suds stabilizers can be a homopolymers, copolymers,terpolymers, etc. of the at least one monomeric unit, or the polymericsuds stabilizer can be copolymers, terpolymers, etc. containing one, twoor more of the at least one monomeric unit and one, two or moremonomeric units other than the at least one monomeric unit. In thecopolymer, terpolymer, etc., the distribution of the monomers can beeither random or repeating.

Some preferred suds stabilizing polymers are homopolymers, copolymers orterpolymers which comprise at least one monomeric units, selected from:

An example of a preferred homopolymer is 2-dimethylaminoethylmethacrylatc (DMAM) having the formula:

Some preferred copolymers include:

copolymers of

An example of a preferred copolymer is the (DMA)/(DMAM) copolymer havingthe general formula:

wherein the ratio of (DMA) to (DMAM) is about 1 to about 10, preferablyabout 1 to about 5, more preferably about 1 to about 3.

An example of a preferred copolymer is the (DMAM)/(DMA) copolymer havingthe general formula:

wherein the ratio of (DMAM) to (DMA) is about 1 to about 5, preferablyabout 1 to about 3.

Another prefered suds stabilizing polymer are the proteinaceous sudsstabilizers. These can be peptides, polypeptides, amino acid containingcopolymers, and mixtures thereof. Any suitable amino acid can be used toform the backbone of the peptides, polypeptides, or amino acidcontaining copolymers of the present invention provided at least 10% toabout 40% of said amino acids which comprise the peptides are capable ofbeing protonated at a pH of from 7 to about 11.5.

In general, the amino acids suitable for use in forming theproteinaceous suds stabilizers of the present invention have from 2 to22 carbon atoms, said amino acids having the formula:

wherein R and R¹ are each independently hydrogen, C₁-C₆ linear orbranched alkyl, C₁-C₆ substituted alkyl, and mixtures thereof. Theindices x and y are each independently from 0 to 2.

An example of a more preferred amino acid according to the presentinvention is the amino acid lysine having the formula:

wherein R is a substituted C₁ alkyl moiety, said substituent is4-imidazolyl.

One type of suitable proteinaceous suds stabilizer is comprised entirelyof amino acids. Said polyamino acid compounds may be naturally occurringpeptides, polypeptides, enzymes, and the like, provided said compoundshave an isoelectric point of from about 7 to about 11.5 and a molecularweight greater than or equal to about 1500 daltons. An example of apolyamino acid which is suitable as a proteinaceous suds stabilizeraccording to the present invention is the enzyme lysozyme.

Another preferred polymeric suds stabilizers are homopolymers orcopolymers wherein the monomers which comprise said homopolymers orcopolymers contain a moiety capable of being protonated at a pH of fromabout 4 to about 12, or a moiety capable of being de-protonated at a pHof from about 4 to about 12, of a mixture of both types of moieties.

A preferred class of zwitterionic polymer suitable for use as a sudsvolume and suds duration enhancer has the formula:

wherein R is C₁-C₁₂ linear alkylene, C₁-C₁₂ branched alkylene, andmixtures thereof; preferably C₁-C₄ linear alkylene, C₃-C₄ branchedalkylene; more preferably methylene and 1,2-propylene. R¹ and R² aredefined herein after. The index x is from 0 to 6; y is 0 or 1; z is 0or 1. The index n has the value such that the zwitterionic polymers ofthe present invention have an average molecular weight of from about1,000 to about 2,000,000 preferably from about 5,000 to about 1,000,000,more preferably from about 10,000 to about 750,000, more preferably fromabout 20,000 to about 500,000, even more preferably from about 35,000 toabout 300,000 daltons. The molecular weight of the polymeric sudsboosters, can be determined via conventional gel permeationchromatography.

Anionic Units—R¹ is a unit capable of having a negative charge at a pHof from about 4 to about 12. Preferred R¹ has the formula:

—(L)_(i)—(S)_(j)—R³

wherein L is a linking unit independently selected from the following:

and mixtures thereof, wherein R¹ is independently hydrogen, C₁-C₄ alkyland mixtures thereof; preferably hydrogen or alternatively R′ and S canform a heterocycle of 4 to 7 carbon atoms, optionally containing otherhetero atoms and optionally substituted. Preferably the linking group Lcan be introduced into the molecule as part of the original monomerbackbone, for example, a polymer having L units of the formula:

can suitably have this moiety introduced into the polymer via acarboxylate containing monomer, for example, a monomer having thegeneral formula:

When the index i is 0, L is absent.

For anionic units S is a “spacing unit” wherein each S unit isindependently selected from C₁-C₁₂ linear alkylene, C₁-C₁₂ branchedalkylene, C₃-C₁₂ linear alkenylene, C₃-C₁₂ branched alkenylene, C₃-C₁₂hydroxyalkylene, C₄-C₁₂ dihydroxyalkylene, C₆-C₁₀ arylene, C₈-C₁₂dialkylarylene, —(R⁵O)_(k)R⁵—, —(R⁵O)_(k)R⁶(OR⁵)_(k)—, —CH₂CH(OR⁷)CH₂—,and mixtures thereof; wherein R⁵ is C₂-C₄ linear alkylene, C₃-C₄branched alkylene, and mixtures thereof, preferably ethylene,1,2-propylene, and mixtures thereof, more preferably ethylene; R⁶ isC₂-C₁₂ linear alkylene, and mixtures thereof, preferably ethylene; R⁷ ishydrogen, C₁-C₄ alkyl, and mixtures thereof, preferably hydrogen. Theindex k is from 1 to about 20.

R³ is independently selected from hydrogen, —CO₂M, —SO₃M, —OSO₃M,—CH₂P(O)(OM)₂, —OP(O)(OM)₂, units having the formula:

—CR⁸R⁹R¹⁰

wherein each R⁸, R⁹, and R¹⁰ is independently selected from the groupconsisting of hydrogen, —(CH₂)_(m)R¹¹, and mixtures thereof, wherein R¹¹is —CO₂H, —SO₃M, —OSO₃M, —CH(CO₂H)CH₂CO₂H, —CH₂P(O)(OH)₂, —OP(O)(OH)₂,and mixtures thereof, preferably —CO₂H, —CH(CO₂H)CH₂CO₂H, and mixturesthereof, more preferably —CO₂H; provided that one R⁸, R⁹, or R¹⁰ is nota hydrogen atom, preferably two R⁸, R⁹, or R¹⁰ units are hydrogen. M ishydrogen or a salt forming cation, preferably hydrogen. The index m hasthe value from 0 to 10.

Cationic Units—R² is a unit capable of having a positive charge at a pHof from about 4 to about 12. Preferred R² has the formula:

—(L¹)_(i′)—(S)_(j′)—R⁴

wherein L¹ is a linking unit independently selected from the following:

and mixtures thereof; wherein R′ is independently hydrogen, C₁-C₄ alkyl,and mixtures thereof; preferably hydrogen or alternatively R′ and S canform a heterocycle of 4 to 7 carbon atoms, optionally containing otherhetero atoms and optionally substituted. When the index i′ is equal to0, L¹ is absent.

For cationic units S is a “spacing unit” wherein each S unit isindependently selected from C₁-C₁₂ linear alkylene, C₁-C₁₂ branchedalkylene, C₃-C₁₂ linear alkenylene, C₃-C₁₂ branched alkenylene, C₃-C₁₂hydroxyalkylene, C₄-C₁₂ dihydroxyalkylene, C₆-C₁₀ arylene, C₈-C₁₂dialkylarylene, —(R⁵O)_(k)R⁵—, —(R⁵O)_(k)R⁶(OR⁵O_(k)—, —CH₂CH(OR⁷)CH₂—,and mixtures thereof; wherein R⁵ is C₂-C₄ linear alkylene, C₃-C₄branched alkylene, and mixtures thereof, preferably ethylene,1,2-propylene, and mixtures thereof, more preferably ethylene; R⁶ isC₂-C₁₂ linear alkylene, and mixtures thereof, preferably ethylene; R⁷ ishydrogen, C₁-C₄ alkyl, and mixtures thereof, preferably hydrogen. Theindex k is from 1 to about 20.

R⁴ is independently selected from amino, alkylamino carboxamide,3-imidazolyl, 4-imidazolyl, 2-imidazolinyl, 4-imidazolinyl,2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1-pyrazolyl, 3-pyrazoyl,4-pyrazoyl, 5-pyrazoyl, 1-pyrazolinyl, 3-pyrazolinyl, 4-pyrazolinyl,5-pyrazolinyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, piperazinyl,2-pyrrolidinyl, 3-pyrrolidinyl, guanidino, amidino, and mixturesthereof, preferably dialkylamino having the formula:

 —N(R¹¹)₂

wherein each R¹¹ is independently hydrogen, C₁-C₄ alkyl, and mixturesthereof, preferably hydrogen or methyl or alternatively the two R¹¹ canform a heterocycle of 4 to 8 carbon atoms, optionally containing otherhetero atoms and optionally substituted.

An example of a preferred zwitterionic polymer according to the presentinvention has the formula:

wherein X is C₆, n has a value such that the average molecular weight isfrom about 5,000 to about 1,000,000 daltons.

Further preferred zwitterionic polymers according to the presentinvention are polymers comprising monomers wherein each monomer has onlycationic units or anionic units, said polymers have the formula:

wherein R, R¹, x, y, and z are the same as defined herein above; n¹+n²=nsuch that n has a value wherein the resulting zwitterionic polymer has amolecular weight of form about 5,000 to about 1,000,000 daltons.

An example of a polymer having monomers with only an anionic unit or acationic unit has the formula:

wherein the sum of n¹ and n² provide a polymer with an average molecularweight of from about 5,000 to about 750,000 daltons.

Another preferred zwitterionic polymer according to the presentinvention are polymers which have limited crosslinking, said polymershaving the formula:

wherein R, R¹, L¹, S, j′, x, y, and z are the same as defined hereinabove; n′ is equal to n″, and the value n′+n″ is less than or equal to5% of the value of n¹+n²=n; n provides a polymer with an averagemolecular weight of from about 1,000 to about 2,000,000 daltons. R¹² isnitrogen, C₁-C₁₂ linear alkylene amino alkylene having the formula:

—R¹³—N—R¹³—

L¹, and mixtures thereof, wherein each R¹³ is independently L¹ orethylene.

The zwitterionic polymers of the present invention may comprise anycombination of monomer units, for example, several different monomershaving various R¹ and R² groups can be combined to form a suitable sudsstabilizer. Alternatively the same R¹ unit may be used with a selectionof different R² units and vice versa.

Furthermore another preferred type of polymeric suds stabilizers arepolymers which contain units capable of having a cationic charge at a pHof from about 4 to about 12, provided that the suds stabilizer has anaverage cationic charge density from about 0.0005 to about 0.05 unitsper 100 daltons molecular weight at a pH of from about 4 to about 12.Additionally, the polymeric suds stabilizer can be present as the freebase or as a salt. Typical counter ions include, citrate, maleate,sulfate, chloride, etc.

For the purposes of the present invention the term “cationic unit” isdefined as “a moiety which when incorporated into the structure of thesuds stabilizers of the present invention, is capable of maintaining acationic charge within the pH range of from about 4 to about 12. Thecationic unit is not required to be protonated at every pH value withinthe range of about 4 to about 12.” Non-limiting examples of units whichcomprise a cationic moiety include lysine, ornithine, the monomeric unithaving the formula:

the monomeric unit having the formula:

the monomeric unit having the formula:

the monomeric unit having the formula:

and the monomeric unit having the formula:

the latter of which also comprises a moiety capable of having an anioniccharge at a pH of about 4 to about 12.

For the purposes of the present invention the term “anionic unit” isdefined as “a moiety which when incorporated into the structure of thesuds stabilizers of the present invention, is capable of maintaining ananionic charge within the pH range of from about 4 to about 12. Theanionic unit is not required to be de-protonated at every pH valuewithin the range of about 4 to about 12.” Non-limiting examples of unitswhich comprise a anionic moiety include, acrylic acid, methacrylic acid,glutamic acid, aspartic acid, the monomeric unit having the formula:

and the monomeric unit having the formula:

the latter of which also comprises a moiety capable of having a cationiccharge at a pH of about 4 to about 12. This latter unit is definedherein as “a unit capable of having an anionic and a cationic charge ata pH of from about 4 to about 12.”

For the purposes of the present invention the term “non-charged unit” isdefined as “a moiety which when incorporated into the structure of thesuds stabilizers of the present invention, has no charge within the pHrange of from about 4 to about 12.” Non-limiting examples of units whichare “non-charged units” are styrene, ethylene, propylene, butylene,1,2-phenylene, esters, amides, ketones, ethers, and the like.

The units which comprise the polymers of the present invention may, assingle units or monomers, have any pK_(a) value.

The formulator may combine any suitable monomers or units to form apolymeric suds stabilizer, for example, amino acids may be combined withpolyacrylate units.

Further information on these and other suitable suds stabilizingpolymers, and processes for their preparation are further described inPCT/US98/24853 filed Nov. 20, 1998, PCT/US98/24707 filed Nov. 20, 1998,PCT/US98/24699 filed Nov. 20, 1998, and PCT/US98/24852 filed Nov. 20,1998.

Enzymes Other than Amylase

The compositions of the present invention may further comprise one ormore enzymes other than amylase which provide cleaning performancebenefits. Said enzymes include enzymes selected from cellulases,hemicellulases, peroxidases, proteases, gluco-amylases, lipases,cutinascs, pectinases, xylanases, reductases, oxidases, phenoloxidases,lipoxygenases, ligninases, pullulanases, tannases, pentosanases,malanases, β-glucanases, arabinosidases or mixtures thereof. A preferredcombination is a detergent composition having a cocktail of conventionalapplicable enzymes like protease, amylase, lipase, cutinase and/orcellulase. Enzymes when present in the compositions, at from about0.0001% to about 5% of active enzyme by weight of the detergentcomposition.

Proteolytic Enzyme—The proteolytic enzyme can be of animal, vegetable ormicroorganism (preferred) origin. The proteases for use in the detergentcompositions herein include (but are not limited to) trypsin,subtilisin, chymotrypsin and elastase-type proteases. Preferred for useherein are subtilisin-type proteolytic enzymes. Particularly preferredis bacterial serine proteolytic enzyme obtained from Bacillus subtilisand/or Bacillus licheniformis.

Suitable proteolytic enzymes include Novo Industri A/S Alcalase®(preferred), Esperase®, Savinase® (Copenhagen, Denmark), Gist-brocades'Maxatase®, Maxacal® and Maxapem 15® (protein engineered Maxacal®)(Delft, Netherlands), and subtilisin BPN and BPN′ (preferred), which arecommercially available. Preferred proteolytic enzymes are also modifiedbacterial serine proteases, such as those made by GenencorInternational, Inc. (San Francisco, Calif.) which are described inEuropean Patent 251,446B, granted Dec. 28, 1994 (particularly pages 17,24 and 98) and which are also called herein “Protease B”. U.S. Pat. No.5,030,378, Venegas, issued Jul. 9, 1991, refers to a modified bacterialserine proteolytic enzyme (Genencor International) which is called“Protease A” herein (same as BPN′). In particular see columns 2 and 3 ofU.S. Pat. No. 5,030,378 for a complete description, including aminosequence, of Protease A and its variants. Other proteases are sold underthe tradenames: Primase, Durazym, Opticlean and Optimase. Preferredproteolytic enzymes, then, are selected from the group consisting ofAlcalase® (Novo Industri A/S), BPN′, Protease A and Protease B(Genencor), and mixtures thereof. Protease B is most preferred.

Of particular interest for use herein are the proteases described inU.S. Pat. No. 5,470,733.

Also proteases described in our co-pending application U.S. Ser. No.08/136,797 can be included in the detergent composition of theinvention.

Another preferred protease, referred to as “Protease D” is a carbonylhydrolase variant having an amino acid sequence not found in nature,which is derived from a precursor carbonyl hydrolase by substituting adifferent amino acid for a plurality of amino acid residues at aposition in said carbonyl hydrolase equivalent to position +76,preferably also in combination with one or more amino acid residuepositions equivalent to those selected from the group consisting of +99,+101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156,+166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265,and/or +274 according to the numbering of Bacillus amyloliquefacienssubtilisin, as described in WO 95/10615 published Apr. 20, 1995 byGenencor International (A. Baeck et al. entitled “Protease-ContainingCleaning Compositions” having U.S. Ser. No. 08/322,676, filed Oct. 13,1994).

Useful proteases are also described in PCT publications: WO 95/30010published Nov. 9, 1995 by The Procter & Gamble Company; WO 95/30011published Nov. 9, 1995 by The Procter & Gamble Company; WO 95/29979published Nov. 9, 1995 by The Procter & Gamble Company.

Protease enzyme may be incorporated into the compositions in accordancewith the invention at a level of from 0.0001% to 2% active enzyme byweight of the composition.

Various carbohydrase enzymes which impart antimicrobial activity mayalso be included in the present invention. Such enzymes includeendoglycosidase, Type II endoglycosidase and glucosidase as disclosed inU.S. Pat. Nos. 5,041,236, 5,395,541, 5,238,843 and 5,356,803 thedisclosures of which are herein incorporated by reference. Of course,other enzymes having antimicrobial activity may be employed as wellincluding peroxidases, oxidases and various other enzymes.

It is also possible to include an enzyme stabilization system into thecompositions of the present invention when any enzyme is present in thecomposition.

Perfumes—Perfumes and perfumery ingredients useful in the presentcompositions and processes comprise a wide variety of natural andsynthetic chemical ingredients, including, but not limited to,aldehydes, ketones, esters, and the like. Also included are variousnatural extracts and essences which can comprise complex mixtures ofingredients, such as orange oil, lemon oil, rose extract, lavender,musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar, andthe like. Finished perfumes can comprise extremely complex mixtures ofsuch ingredients. Finished perfumes typically comprise from about 0.01%to about 2%, by weight, of the detergent compositions herein, andindividual perfumery ingredients can comprise from about 0.0001% toabout 90% of a finished perfume composition.

Non-limiting examples of perfume ingredients useful herein include:7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene;ionone methyl; ionone gamma methyl; methyl cedrylone; methyldihydrojasmonate; methyl 1,6,10-trimethyl-2,5,9-cyclododecatrien-1-ylketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;4-acetyl-6-tert-butyl-1,1-dimethyl indane; para-hydroxy-phenyl-butanone;benzophenone; methyl beta-naphthyl ketone;6-acetyl-1,1,2,3,3,5-hexamethyl indane;5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal,4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde;7-hydroxy-3,7-dimethyl ocatanal; 10-undecen-1-al; iso-hexenyl cyclohexylcarboxaldehyde; formyl tricyclodecane; condensation products ofhydroxycitronellal and methyl anthranilate, condensation products ofhydroxycitronellal and indol, condensation products of phenylacetaldehyde and indol;2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; ethyl vanillin;heliotropin; hexyl cinnamic aldehyde; amyl cinnamic aldehyde;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; coumarin;decalactone gamma; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acidlactone;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyrane;beta-naphthol methyl ether; ambroxane;dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1b]furan; cedrol,5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol;2-ethyl-4-2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol;caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenylacetate; benzyl salicylate; cedryl acetate; and para-(tert-butyl)cyclohexyl acetate.

Particularly preferred perfume materials are those that provide thelargest odor improvements in finished product compositions containingcellulases. These perfumes include but are not limited to: hexylcinnamic aldehyde; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde;7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene;benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate;beta-napthol methyl ether; methyl betanaphthyl ketone;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyrane;dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1b]furan; anisaldehyde;coumarin; cedrol; vanillin; cyclopentadecanolide; tricyclodecenylacetate; and tricyclodecenyl propionate.

Other perfume materials include essential oils, resinoids, and resinsfrom a variety of sources including, but not limited to: Peru balsam,Olibanum resinoid, styrax, labdanum resin, nutmeg, cassia oil, benzoinresin, coriander and lavandin. Still other perfume chemicals includephenyl ethyl alcohol, terpineol, linalool, linalyl acetate, geraniol,nerol, 2-(1,1-dimethylethyl)-cyclohexanol acetate, benzyl acetate, andeugenol. Carriers such as diethylphthalate can be used in the finishedperfume compositions.

Dispersant Polymers

The compositions used in the methods of the present invention may alsooptionally contain from about 0.1% to about 20%, more preferably fromabout 0.5% to about 10% by weight of the composition of a dispersantpolymer. Dispersant polymers are compounds which act as soil suspendingagents in the aqueous wash liquor. That is, they act to suspend thesoils in solution and prevent the soils from re-depositing on thesurfaces of fabrics or dishes. This allows soils to be removed with thewash liquor. Dispersant polymers are well-known and conventional and areavailable from BASF Corp. and Rohm & Haas. Typical examples includepolyethoxylated amines and acrylic acid/maleic acid copolymers.

Soil Release Agents

The compositions according to the present invention may optionallycomprise one or more soil release agents. Polymeric soil release agentsare characterized by having both hydrophilic segments, to hydrophilizethe surface of hydrophobic fibers, such as polyester and nylon, andhydrophobic segments, to deposit upon hydrophobic fibers and remainadhered thereto through completion of the laundry cycle and, thus, serveas an anchor for the hydrophilic segments. This can enable stainsoccuring subsequent to treatment with the soil release agent to be moreeasily cleaned in later washing procedures.

If utilized, soil release agents will generally comprise from about0.01% to about 10% preferably from about 0.1% to about 5%, morepreferably from about 0.2% to about 3% by weight, of the composition.

The following, all included herein by reference, describe soil releasepolymers suitable for us in the present invention. U.S. Pat. No.5,691,298 Gosselink et al., issued Nov. 25, 1997; U.S. Pat. No.5,599,782 Pan et al., issued Feb. 4, 1997; U.S. Pat. No. 5,415,807Gosselink et al., issued May 16, 1995; U.S. Pat. No. 5,182,043 Morrallet al., issued Jan. 26, 1993; U.S. Pat. No. 4,956,447 Gosselink et al.,issued Sep. 11, 1990; U.S. Pat. No. 4,976,879 Maldonado et al. issuedDec. 11, 1990; U.S. Pat. No. 4,968,451 Scheibel et al., issued Nov. 6,1990; U.S. Pat. No. 4,925,577 Borcher, Sr. et al., issued May 15, 1990;U.S. Pat. No. 4,861,512 Gosselink, issued Aug. 29, 1989; U.S. Pat. No.4,877,896 Maldonado et al., issued Oct. 31, 1989; U.S. Pat. No.4,771,730 Gosselink et al., issued Oct. 27, 1987; U.S. Pat. No. 711,730Gosselink et al., issued Dec. 8, 1987; U.S. Pat. No. 4,721,580 Gosselinkissued Jan. 26, 1988; U.S. Pat. No. 4,000,093 Nicol et al., issued Dec.28, 1976; U.S. Pat. No. 3,959,230 Hayes, issued May 25, 1976; U.S. Pat.No. 3,893,929 Basadur, issued Jul. 8, 1975; and European PatentApplication 0 219 048, published Apr. 22, 1987 by Kud et al.

Further suitable soil release agents are described in U.S. Pat. No.4,201,824 Voilland et al.; U.S. Pat. No. 4,240,918 Lagasse et al.; U.S.Pat. No. 4,525,524 Tung et al.; U.S. Pat. No. 4,579,681 Ruppert et al.;U.S. Pat. No. 4,220,918; U.S. Pat. No. 4,787,989; EP 279,134 A, 1988 toRhone-Poulenc Chemie; EP 457,205 A to BASF (1991); and U.S. Pat. No. DE2,335,044 to Unilever N. V., 1974; all incorporated herein by reference.

Brightener

Any optical brighteners or other brightening or whitening agents knownin the art can be present at levels typically from about 0.05% to about1.2%, by weight, in the compositions used herein. Commercial opticalbrighteners which may be useful in the present invention can beclassified into subgroups, which include, but are not necessarilylimited to, derivatives of stilbene, pyrazoline, coumarin, carboxylicacid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5-and6-membered-ring heterocycles, and other miscellaneous agents. Examplesof such brighteners are disclosed in “The Production and Application ofFluorescent Brightening Agents”, M. Zahradnik, Published by John Wiley &Sons, New York (1982).

Specific examples of optical brighteners which are useful in the presentcompositions are those identified in U.S. Pat. No. 4,790,856, issued toWixon on Dec. 13, 1988. These brighteners include the PHORWHITE seriesof brighteners from Verona. Other brighteners disclosed in thisreference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; availablefrom Ciba-Geigy; Artic White CC and Artic White CWD, available fromHilton-Davis, located in Italy; the2-(4-stryl-phenyl)-2H-napthol[1,2-d]triazoles;4,4′-bis-(1,2,3-trazol-2-yl)-stil-benes; 4,4′-bis(stryl)bisphenyls; andthe aminocoumarins. Specific examples of these brighteners include4-methyl-7-diethyl-amino coumarin; 1,2-bis(-venzimidazol-2-yl)ethylene;1,3-diphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene;2-stryl-napth-[1,2-d]oxazole; and2-(stilbene-4-yl)-2H-naphtho-[1,2-d]triazole. See also U.S. Pat. No.3,646,015, issued Feb. 29, 1972 to Hamilton. Anionic brighteners arepreferred herein.

Other Ingredients—The compositions can further preferably comprise oneor more detersive adjuncts selected from the following: polysaccharides,abrasives, bactericides, tarnish inhibitors, dyes, buffers, antifungalor mildew control agents, insect repellents, perfumes, thickeners,processing aids, anti-corrosive aids, stabilizers and antioxidants. Awide variety of other ingredients useful in detergent compositions canbe included in the compositions herein, including other activeingredients, carriers, antioxidants, processing aids, dyes or pigments,solvents for liquid formulations, etc.

Usual ingredients can include one or more materials for assisting orenhancing cleaning performance, treatment of the substrate to becleaned, or to modify the aesthetics of the composition. Usual detersiveadjuncts of detergent compositions include the ingredients set forth inU.S. Pat. No. 3,936,537, Baskerville et al. Adjuncts which can also beused in the compositions employed in the present invention, in theirconventional art-established levels for use (generally from 0% to about20% of the detergent ingredients, preferably from about 0.5% to about10%), include other active ingredients such as enzyme stabilizers, colorspeckles, anti-tarnish and/or anti-corrosion agents, dyes, fillers,optical brighteners, germicides, alkalinity sources, anti-oxidants,enzyme stabilizing agents, perfumes, dyes, solubilizing agents, claysoil removal/anti-redeposition agents, carriers, processing aids,pigments, solvents for liquid formulations, fabric softeners, staticcontrol agents, etc. Dye transfer inhibiting agents, including polyamineN-oxides such as polyvinylpyridine N-oxide can be used.Dye-transfer-inhibiting agents are further illustrated bypolyvinylpyrrolidone and copolymers of N-vinyl imidazole and N-vinylpyrrolidone. If desired, soluble magnesium salts such as MgCl₂, MgSO₄,and the like, can be added at levels of, typically, 0.1%-C2%, to enhancegrease removal performance.

Various detersive ingredients employed in the present compositionsoptionally can be further stabilized by absorbing said ingredients ontoa porous hydrophobic substrate, then coating said substrate with ahydrophobic coating. Preferably, the detersive ingredient is admixedwith a surfactant before being absorbed into the porous substrate. Inuse, the detersive ingredient is released from the substrate into theaqueous washing liquor, where it performs its intended detersivefunction.

To illustrate this technique in more detail, a porous hydrophobic silica(trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzymesolution containing 3%-5% of C₁₃₋₁₅ ethoxylated alcohol (EO 7) nonionicsurfactant. Typically, the enzyme/surfactant solution is 2.5× the weightof silica. The resulting powder is dispersed with stirring in siliconeoil (various silicone oil viscosities in the range of 500-12,500 can beused). The resulting silicone oil dispersion is emulsified or otherwiseadded to the final detergent matrix. By this means, ingredients such asthe aforementioned enzymes, bleaches, bleach activators, bleachcatalysts, photoactivators, dyes, fluorescers, fabric conditioners andhydrolyzable surfactants can be “protected” for use in detergentcompositions.

An antioxidant can be optionally added to the detergent compositions ofthe present invention. They can be any conventional antioxidant used indetergent compositions, such as 2,6-di-tert-butyl-4-methylphenol (BHT),carbamate, ascorbate, thiosulfate, monoethanolamine(MEA),diethanolamine, triethanolamine, etc. It is preferred that theantioxidant, when present, be present in the composition from about0.001% to about 5% by weight.

The compositions of this invention can be in any form, including liquid,tablet, paste, gel, microemulsion or tricritical composition. Highlypreferred embodiments are in liquid or gel form. Liquid detergentcompositions can contain water and other solvents as carriers. Lowmolecular weight primary or secondary alcohols exemplified by methanol,ethanol, propanol, and isopropanol are suitable. Monohydric alcohols arepreferred for solubilizing surfactant, but polyols such as thosecontaining from 2 to about 6 carbon atoms and from 2 to about 6 hydroxygroups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and1,2-propanediol) can also be used. The compositions may contain from 5%to 90%, typically 10% to 50% of such carriers.

An example of the procedure for making liquid compositions herein is asfollows:—To the free water and citrate are added and dissolved. To thissolution amine oxide, betaine, ethanol, hydrotrope and nonionicsurfactant are added. If free water isn't available, the citrate areadded to the above mix then stirred until dissolved. At this point, anacid is added to neutralize the formulation. It is preferred that theacid be chosen from organic acids such as maleic and citric, however,inorganic mineral acids may be employed as well. In preferredembodiments these acids are added to the formulation followed by diamineaddition. AExS is added last.

Compositions of the invention will have a pH range of from about 2 toabout 13, preferably, pH is alkaline, more preferably from about 7 toabout 12.5, more preferably from about 8 to about 12, even morepreferably from about 9 to about 11.5.

EXAMPLES

The following Examples further illustrate the present invention, but arenot intended to be limiting thereof.

Ultrasonic energy greatly enhanced starch soil removal and is synergeticwith the use of amylase.

% Starch Removal (46° C., 7 gpg) 5 min ultrasonic Treatment soak 5 min.soak 3% pc Ultrasonic Bath Soak + ADW Rinse Composition 1 (see 42  2below) Composition 1 + 98 44 amylase enzyme* (1.5 ppm TTW) (i) ADWrinse: European miniwasher, short (5 min.) ramp up to 44° C., 7 gpg (ii)Ultrasonic Bath (no presoak): 2 starch coupons suspended in the middleof a Branson 2210 Sonic cleaner (iii) 1.5 ppm TTW corresponds to 0.005%amylase in product (iv) The ultrasonic energy used here is ˜50-70 watts.

Ultrasonics enhances the performance of bleach catalyst bleaching systemon tea stain under short soak times. The addition of ultrasonicsprovides minimal cleaning benefits to tea stain removal using LDL3.

Tea Stained Mug Grade (scale 1-10; worst-best) 2 minutes 5 minutesultrasonic ultrasonic Treatments soak soak soak soak LDL3, 3% pc 2 4.8 35 ADW composition 5 9 7.5 n/a (3000 ppm TTW) (i) Soak conditions: 46 C.,400 rpm, 7 gpg, 250 ml volume (ii) Ultrasonic soak conditions: 46 C., 7gpg, Branson ultrasonic bath Model 2210, 250 ml volume (iii) Contains0.004% Acetatopentaamine cobalt (0.24 ppm TTW in this test)

Direct contact of transducer to soil is the approach being used for thedesign of the hand held implement.

% Egg soil removal (0.4% product Treatments concentration 2S) Soak + ADWRinse 22 Coupon suspended in middle of the bath 45 Coupon in contactwith transducer 66 ¹ Branson 2210 Ultrasonic cleaner, 46° C., 7 gpg

Pasta Soil Removal

Significant cleaning occurs with the ultrasonic implement after 7controlled strokes on pasta soil. The weight of the implement nilultrasonic energy removes more soil than a Scotch-Brite pad alone.

% Pasta Soil Conditions (composition 1 + 0.005% Amylase, ˜40 C.) Removal7 strokes with a Scotch-Brite pad (nil ultrasound) 30 7 strokes withultrasonic implement (+ ultrasound) 86 7 strokes with ultrasonicimplement (− ultrasound) 48 Each condition was an average of 2 coupons

Composition of uses in this test

Composition Composition 1 2 10% pH 7.8 10.0 AE0.6S 26.28 29.0 Amineoxide 1.73 7.5 ADM Betaine 1.73 — C11E9 — 4.88 C10E8 4.56 — NN, dialkyl1.37 — glucamine Diamine — 4.88 Mg++ 0.46 — ADW composition % Phosphate25.47 Carbonate 30.50 Sulfate 20.19 Silicate 5.69 Nonionic 1.84surfactant Perborate 4.34 protease enzyme 0.90 PAAN 0.004 Water,perfume, qs to minors etc., 100%

What is claimed is:
 1. An ultrasonic cleaning product comprising: (a) acleaning composition comprising an ultrasonically enhanced cleaningagent comprising cobalt bleach catalyst; and, (b) a sonic or ultrasonicwave generating source for imparting sonic or ultrasonic waves.
 2. Theultrasonic cleaning product of claim 1 wherein the ultrasonicallyenhanced cleaning agent is present in the cleaning composition fromabout 0.0001% to about 40% by weight.
 3. The ultrasonic cleaning productof claim 1 wherein said cleaning composition further comprises aconventional cleaning adjunct, said adjunct is selected from the groupconsisting of builders, surfactants, enzymes other than amylase, bleachactivators, bleach boosters, bleaches, alkalinity sources, colorants,perfume, antibacterial agent, lime soap dispersants, polymeric dyetransfer inhibiting agents, crystal growth inhibitors, photobleaches,heavy metal ion sequestrants, anti-tarnishing agents, anti-microbialagents, anti-oxidants, anti-redeposition agents, soil release polymers,electrolytes, pH modifiers, thickeners, abrasives, metal ion salts,enzyme stabilizers, corrosion inhibitors, diamines, suds stabilizingpolymers, solvents, process aids, fabric softening agents, opticalbrighteners, hydrotropes, and mixtures thereof.
 4. The process of claim1 wherein said sonic or ultrasonic source is a hand-held vibrationalultrasonic device with a cleaning head on a distal end of said device.5. The ultrasonic cleaning product of claim 1 wherein said liquidcleaning composition and said sonic or ultrasonic source are containedtogether in a device that permits controlled dispensing of said liquidcleaning composition to a hard surface in need of cleaning whileconcurrently imparting sonic or ultrasonic waves to said hard surface.6. The ultrasonic cleaning product of claim 1 further comprisinginstructions for using said product comprising the steps of: (i)applying an effective amount of said cleaning composition to said hardsurface; and (ii) imparting sonic or ultrasonic waves to said surfaceusing said sonic or ultrasonic source.
 7. The ultrasonic cleaningproduct of claim 6 comprising further instructions for using saidproduct comprising the steps of: (iii) using said device to apply aneffective amount of said cleaning composition to said hard surfaceconcurrently with sonic or ultrasonic waves from said sonic orultrasonic source; and (iv) moving said sonic or ultrasonic source oversaid hard surface while maintaining contact with said hard surface.
 8. Aprocess for removing tough food from a hard surface comprising the stepsof: (a) applying an effective amount of a cleaning composition to saidtough food on said hard surface, said liquid cleaning compositioncomprises an ultrasonically enhanced cleaning agent comprising cobaltbleach catalyst; and (b) imparting sonic or ultrasonic waves to saidtough food so as to remove said tough food from said hard surface. 9.The process of claim 8 wherein said sonic or ultrasonic source is ahand-held vibrational ultrasonic device with a cleaning head on a distalend of said device.
 10. The process of claim 8 wherein said steps (a)and (b) are conducted simultaneously using a device that permitscontrolled dispensing of said liquid cleaning composition to said toughfood while concurrently imparting sonic or ultrasonic waves to saidtough food.
 11. The process of claim 8 wherein said wherein saidcleaning composition further comprises a conventional cleaning adjunct,said adjunct is selected from the group consisting of builders,surfactants, enzymes, bleach activators, antibacterial agent, bleachcatalysts, bleach boosters, bleaches, alkalinity sources, colorants,perfume, lime soap dispersants, polymeric dye transfer inhibitingagents, crystal growth inhibitors, photobleaches, heavy metal ionsequestrants, anti-tarnishing agents, anti-microbial agents,anti-oxidants, anti-redeposition agents, soil release polymers,electrolytes, pH modifiers, thickeners, abrasives, metal ion salts,enzyme stabilizers, corrosion inhibitors, diamines, suds stabilizingpolymers, solvents, process aids, fabric softening agents, opticalbrighteners, hydrotropes, and mixtures thereof.
 12. The process of claim8 wherein said process comprises the further step of: (c) rinsing saidhard surface with an aqueous solution.
 13. An ultrasonic cleaningproduct according to claim 1 wherein said ultrasonically enhancedcleaning agent further comprises an amylase enzyme.
 14. An ultrasoniccleaning product according to claim 1 wherein said ultrasonicallyenhanced cleaning agent further comprises a bleach catalyst selectedfrom the group consisting of manganese bleach catalyst, iron bleachcatalyst, and mixtures thereof.
 15. A process according to claim 8wherein said ultrasonically enhanced cleaning agent further comprises anamylase enzyme.
 16. A process according to claim 8 wherein saidultrasonically enhanced cleaning agent further comprises a bleachcatalyst selected from the group consisting of manganese bleachcatalyst, iron bleach catalyst, and mixtures thereof.